Thiazole-4-Carboxylic Acid Esters and Thioesters as Plant Protection Agents

ABSTRACT

The use of thiazole-4-carboxylic esters and thioesters of the formula (I) 
     
       
         
         
             
             
         
       
     
     in which
         R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , Y 1 , Y 2 , Y 3 , W, X and G have the meanings given in the description, and also of agrochemically active salts thereof, as fungicides.

The invention relates to thiazole-4-carboxylic esters and thioesters oragrochemically active salts thereof, to their use and to methods andcompositions for controlling phytopathogenic harmful fungi in and/or onplants or in and/or on seed of plants, to processes for preparing suchcompositions and to treated seed, and to their use for controllingphytopathogenic harmful fungi in agriculture, horticulture and forestry,in animal health, in the protection of materials and in the domestic andhygiene field. The present invention furthermore relates to a processfor preparing thiazole-4-carboxylic esters and thioesters.

It is already known that certain piperidinyl-substitutedthiazole-4-carboxamides can be used as fungicidal crop protection agents(see WO 07/014,290, WO08/091,594). However, in particular at relativelylow application rates, the fungicidal activity of these compounds is notalways sufficient. Furthermore, in many cases the activity spectrum ofthese amides is insufficient. Moreover, some carboxylic esters aredescribed as intermediates; however, a biological activity is notdescribed.

WO 04/058751 describes piperidinyl-substituted thiazole-4-carboxylicesters and thioesters which can be used as pharmaceutics for modulatingblood pressure.

WO 05/003128 describes further piperidinyl-substitutedthiazole-4-carboxylic esters and thioesters which are likewise suitablefor medicinal applications, here as inhibitors on the microsomaltriglyceride transfer protein (MTP inhibitors). However, an effect onfungal pathogens is not described.

Since the ecological and economical demands made on modern cropprotection agents are increasing constantly, for example with respect toactivity spectrum, toxicity, selectivity, application rate, formation ofresidues and favorable manufacture, and there can furthermore beproblems, for example, with resistances, there is a constant need todevelop novel crop protection agents which, at least in some areas, haveadvantages over the known ones.

Surprisingly, it has now been found that the presentthiazole-4-carboxylic esters and thioesters achieve at least someaspects of the objects mentioned and are suitable for use as cropprotection agents, in particular as fungicides.

The invention relates to compounds of the formulas (I)

in which the symbols have the following meanings:

-   R¹ and R³ independently of one another are H, C₁-C₄-alkyl,    C₂-C₄-alkenyl, C₂-C₄-alkynyl, C₃-C₆-cycloalkyl,    C₃-C₆-halocycloalkyl, optionally substituted phenyl, C₁-C₄-alkoxy,    C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, (C₁-C₄-alkyl)carbonyl, formyl,    CR⁸═NOR⁹, CONR¹⁰R¹¹, (C₁-C₄-alkoxy)carbonyl, COOH, halogen, hydroxyl    or cyano-   R² is H, substituted or unsubstituted phenyl, C₁-C₄-alkyl,    C₂-C₄-alkenyl, C₂-C₄-alkynyl, C₃-C₆-cycloalkyl,    C₃-C₆-halocycloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl,    C₁-C₄-haloalkoxy, (C₁-C₄-alkyl)carbonyl, formyl, CR⁸═NOR⁹,    CONR¹⁰R¹¹, (C₁-C₄-alkoxy)carbonyl, COOH, halogen, hydroxyl, cyano,    nitro or NR¹⁰R¹¹    or-   R¹ and R² or R² and R³ together with the carbon atoms to which they    are attached form a 5- to 7-membered unsubstituted or substituted,    partially saturated or unsaturated cycle which may contain up to    three further heteroatoms selected from the group consisting of N, O    and S, where two oxygen atoms are not adjacent,    possible substituents independently of one another being selected    from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, oxo,    hydroxyl and halogen-   R⁴ and R⁵ independently of one another are H, C₁-C₄-alkyl,    C₃-C₆-cycloalkyl or C₁-C₄-haloalkyl,    or-   R⁴ and R⁵ together with the carbon atom to which they are attached    form a 3- to 7-membered unsubstituted or substituted saturated cycle    which may contain up to three heteroatoms selected from the group    consisting of N, O and S, where two oxygen atoms are not adjacent,    possible substituents independently of one another being selected    from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, oxo,    hydroxyl, halogen-   Y¹, Y², Y³ independently of one another are sulfur or oxygen-   X is a direct bond or an unsubstituted or substituted C₁- to    C₃-carbon chain, where the carbon atoms carry, independently of one    another, H, C₁-C₄-alkyl or oxo as substituents-   W is an unsubstituted or substituted C₁- to C₃-carbon chain, where    the carbon atoms carry, independently of one another, H, C₁-C₄-alkyl    or oxo as substituents-   R⁶ is H, C₁-C₄-alkyl, C₁-C₄-haloalkyl, (C₁-C₄-alkyl)carbonyl,    formyl, CR⁸═NOR⁹, CONR¹⁰R¹¹, (C₁-C₄-alkoxy)carbonyl, COOH, NR¹⁰R¹¹,    nitro, halogen or cyano-   G is (C(R¹²)₂)_(m)    where m=0 to 6-   R⁷ is unsubstituted or substituted C₅-C₁₀-alkyl, C₂-C₁₆-alkenyl,    C₂-C₁₆-alkynyl, C₃-C₁₅-cycloalkyl, C₅-C₁₅-cycloalkenyl,    C₃-C₁₅-heterocyclyl, aryl, hetaryl or Si(C₁-C₄-alkyl)₃,    possible substituents independently of one another being selected    from the list below:-   halogen, cyano, nitro, nitroso, C₁-C₄-haloalkyl, arylalkyl,    arylhaloalkyl, hydroxyl, oxo, C₁-C₄-alkoxy,    O(C₁-C₆-alkyl)_(m)OC₁-C₆-alkyl, O—C₃-C₆-cycloalkyl, O-phenyl,    C₁-C₄-haloalkoxy, SH, C₁-C₆-thioalkyl, C₁-C₆-thiohaloalkyl,    S-phenyl, SO₂—C₁-C₆-alkyl, SO₂—C₁-C₆-haloalkyl, SO—C₁-C₆-alkyl,    SO—C₁-C₆-haloalkyl, CO₂H, (C₁-C₄-alkyl)carbonyl,    (C₁-C₄-haloalkyl)carbonyl, formyl, CR⁸═NOR⁹, CONR¹⁰R¹¹,    (C₁-C₄-alkoxy)carbonyl, COOH, NR¹⁰R¹¹, cyclopropylamino, CH₂COCH₃,    (CH₂)_(m)O—C₁-C₆-alkyl, CH₂OH, CH₂SMe, (CH₂)₂SMe, C₃-C₆-cycloalkyl,    1-methoxycyclopropyl, 1-chlorocyclopropyl, cyclohexylmethyl,    C₂-C₆-alkenyl, C₂-C₆-alkynyl, Si(C₁-C₄-alkyl)₃, phenyl or benzyl    or    two adjacent substituents form an optionally methyl- or    halogen-substituted dioxolane or dioxane ring,-   R⁸, R⁹, R¹⁰, R¹¹ independently of one another are H, C₁-C₄-alkyl or    C₃-C₆-cycloalkyl,    or-   R¹⁰ and R¹¹ together with the nitrogen atom to which they are    attached form a 3- to 7-membered unsubstituted or substituted    saturated cycle which may contain up to two further heteroatoms    selected from the group consisting of N, O and S, where two oxygen    atoms are not adjacent,    possible substituents independently of one another being selected    from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen and    oxo-   R¹² is identical or different independently of one another H,    halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₃-C₆-cycloalkyl or    C₁-C₄-haloalkyl,    or    two or four R¹², in each case on two adjacent carbon atoms, are    direct bonds,    and also agrochemically active salts thereof.

The thiazole-4-carboxylic esters and thioesters of the formula (I)according to the invention and their agrochemically active salts arehighly suitable for controlling phytopathogenic harmful fungi. Thecompounds according to the invention mentioned above have potentfungicidal activity and can be used both in crop protection, in thedomestic and hygiene field and in the protection of materials.

The compounds of the formula (I) can be present both in pure form and asmixtures of various possible isomeric forms, in particular ofstereoisomers, such as E and Z, threo and erythro, endo or exo, and alsooptical isomers, such as R and S isomers or atropisomers, and, ifappropriate, also of tautomers. What is claimed are both the E and the Zisomers, and also the threo and erythro, and also the optical isomers,any mixtures of these isomers, and also the possible tautomeric forms.

Preference is given to compounds of the formula (I) in which one or moreof the symbols have one of the meanings below:

-   R¹ and R³ independently of one another are H, C₁-C₄ alkyl    C₃-C₆-cycloalkyl, C₁-C₃-alkoxy, C₁-C₃-haloalkyl, C₁-C₃-haloalkoxy,    halogen, hydroxyl, cyano or phenyl,-   R² is H, phenyl, C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-alkynyl,    C₃-C₆-cycloalkyl, C₁-C₃-alkoxy, C₁-C₃-haloalkyl, C₁-C₃-haloalkoxy,    halogen, hydroxyl, cyano or NR¹⁰R¹¹,    or-   R¹ and R² together with the carbon atoms to which they are attached    form a phenyl ring,-   R⁴ and R⁵ independently of one another are H, C₁-C₃-alkyl,    cyclopropyl, cyclopentyl, cyclohexyl, or C₁-C₃-haloalkyl,    or-   R⁴ and R⁵ together with the carbon atom to which they are attached    form a cyclopropyl ring,-   Y¹ and Y² are oxygen,-   Y³ is sulfur or oxygen,-   X is a direct bond, CH₂ or CH₂CH₂,-   W is CH₂, CH₂CH₂ or CH₂CH₂CH₂,-   R⁶ is H, C₁-C₃-alkyl, C₁-C₃-haloalkyl, NH₂, NHMe, NMe₂, chlorine,    fluorine or cyano,-   G is (C(R₁₂)₂)_(m)    where m=0 to 4-   R⁷ is unsubstituted or substituted C₅-C₁₀-alkyl, C₂-C₁₆-alkenyl,    C₂-C₁₆-alkynyl, C₃-C₁₅-cycloalkyl, C₅-C₁₅-cycloalkenyl,    C₃-C₁₅-heterocyclyl, aryl, hetaryl or Si(C₁-C₄-alkyl)₃,    possible substituents independently of one another being selected    from the list below:-   fluorine, chlorine, bromine, iodine, cyano, nitro, CF₃, CFH₂, CF₂H,    C₂F₅, CCl₃, hydroxyl, OMe, OEt, OPr, OisoPr, OBu, OsecBu, OisoBu,    OtertBu, O(CH₂)₂OCH₃, O(CH₂)₃OCH₃, O-cyclohexyl, O-cyclopentyl,    O-cyclopropyl, O-phenyl, OCF₃, OCF₂H, OCH₂CF₃, OCF₂CF₃, SH, SMe,    SEt, SCF₃, SCF₂H, S-phenyl, SO₂Me, SO₂CF₃, SOMe, SOEt, CO₂H, CO₂CH₃,    CO₂Et, CO₂Pr, CO₂isoPr, CO₂tertBu, COMe, COCF₃, NH₂, NHMe, NMe₂,    NHEt, NEt₂, NHPr, NHisoPr, NHnBu, NHtertBu, NHisoBu, NHsecBu,    cyclopropylamino, morpholinyl, piperidinyl, piperazinyl,    pyrrolidinyl, aziridinyl, azetidinyl, formyl, CH₂COCH₃, CH₂OMe,    (CH₂)₂OMe, (CH₂)₃OMe, CH₂OH, CH₂SMe, (CH₂)₂SMe, methyl, ethyl,    propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl,    1,1-dimethylethyl, 1-methoxycyclopropyl, 1-chlorocyclopropyl,    cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl,    prop-2-en-1-yl, 1-methylprop-2-en-1-yl, but-3-en-1-yl,    trimethylsilyl)methyl, phenyl, benzyl, —CH═CH₂, —CH₂CH═CH₂,    —CH(CH₃)CH═CH₂, —CH₂C≡CH, —C≡CH,    or    two adjacent substituents form an optionally methyl- or    halogen-substituted dioxolane or dioxane ring,-   R¹⁰, R¹¹ independently of one another are H, methyl, ethyl,    isopropyl or cyclopropyl,    or-   R¹⁰ and R¹¹ together with the nitrogen atom to which they are    attached form an aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl    or morpholinyl ring,-   R¹² is identical or different independently of one another H,    methyl, ethyl, chlorine, fluorine, trifluoromethyl, methoxy or    cyclopropyl,    or    two or four R¹², in each case on two adjacent carbon atoms, are    direct bonds,    and the agrochemically active salts thereof.

Particular preference is given to compounds of the formula (I) in whichone or more of the symbols have one of the meanings below:

-   R¹ is C₁-C₂-alkyl or C₁-C₂-haloalkyl,-   R² is H, C₁-C₂-haloalkyl or halogen,    or-   R¹ and R² together with the carbon atoms to which they are attached    form a phenyl ring,-   R³ is H, C₁-C₂-alkyl, C₁-C₂-haloalkyl or phenyl,-   R⁴ is H, C₁-C₂-alkyl or C₁-C₂-haloalkyl,-   R⁵ is H, C₁-C₂-alkyl, C₁-C₂-haloalkyl or cyclopropyl,    or-   R⁴ and R⁵ together with the carbon atom to which they are attached    form a cyclopropyl ring,-   Y¹ is oxygen,-   Y² is oxygen,-   Y³ is sulfur or oxygen,-   X is CH₂ or CH₂CH₂,-   W is CH₂, CH₂CH₂ or CH₂CH₂CH₂,-   R⁶ is H or methyl,-   G is (C(R¹²)₂),    where m=0 to 4-   R⁷ is unsubstituted or substituted C₅-C₁₀-alkyl, C₂-C₁₆-alkenyl,    C₂-C₁₆-alkynyl, C₃-C₁₅-cycloalkyl, C₅-C₁₅-cycloalkenyl,    C₃-C₁₅-heterocyclyl, aryl, hetaryl or Si(C₁-C₄-alkyl)₃,    possible substituents independently of one another being selected    from the list below:-   fluorine, chlorine, bromine, iodine, cyano, nitro, CF₃, hydroxyl,    OMe, O-phenyl, OCF₃, OCF₂H, OCH₂CF₃, OCF₂CF₃, SMe, S-phenyl, methyl,    ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl,    1,1-dimethylethyl, phenyl, benzyl, —CH═CH₂, —CH₂CH═CH₂ or —C≡CH,-   R¹² is identical or different independently of one another H, methyl    or ethyl,    and the agrochemically active salts thereof.

Very particular preference is given to compounds of the formula (I) inwhich one or more of the symbols have one of the meanings below:

-   R¹ is methyl, ethyl, 1-methylethyl, 1,1-dimethylethyl,    difluoromethyl, trifluoromethyl or pentafluoroethyl,-   R² is H or chlorine,    or-   R¹ and R² together with the carbon atoms to which they are attached    form a phenyl ring,-   R³ is H, methyl, 1,1-dimethylethyl, difluoromethyl, trifluoromethyl,    pentafluoroethyl or phenyl,-   R⁴ is H or methyl,-   R⁵ is H, methyl or cyclopropyl,    or-   R⁴ and R⁵ together with the carbon atom to which they are attached    form a cyclopropyl ring,-   Y¹ is oxygen,-   Y² is oxygen,-   Y³ is sulfur or oxygen,-   X is CH₂ or CH₂CH₂,-   W is CH₂, CH₂CH₂ or CH₂CH₂CH₂,-   R⁶ is H or methyl,-   G is a direct bond, CH₂, CH₂CH₂, CH(CH₃), CH(CH₂CH₃) or CH(CF₃),-   R⁷ is methyl, tert-butyl, heptan-3-yl, octyl, (1Z)-prop-1-en-1-yl,    (E)-2-phenylethenyl, hex-1-en-3-yl, diphenylmethyl,    1,2,3,4-tetrahydronaphthalen-1-yl,    (1R)-1,2,3,4-tetrahydronaphthalen-1-yl,    (1S)-1,2,3,4-tetrahydronaphthalen-1-yl,    1,2,3,4-tetrahydronaphthalen-2-yl,    5,6,7,8-tetrahydronaphthalen-1-yl,    5,6,7,8-tetrahydronaphthalen-2-yl, decahydronaphthalen-1-yl,    1,4-dioxaspiro[4.5]dec-8-yl, 2,3-dihydro-1H-inden-1-yl,    2,3-dihydro-1H-inden-2-yl, cyclopropyl, 2,2-dichlorocyclopropyl,    cyclopentyl, 1-ethynylcyclopentyl, cyclohexyl, 2-methylcyclohexyl,    2,6-dimethylcyclohexyl, 4-tert-butylcyclohexyl,    5-methyl-2-(propan-2-yl)cyclohexyl,    3-methyl-5-(propan-2-yl)cyclohexyl, 1-cyanocyclohexyl,    1-ethynylcyclohexyl, cycloheptyl, cyclopropyl(phenyl)methyl,    (1S,2R)-1,7,7-trimethylbicyclo[2.2.1]hept-2-yl, phenyl,    4-fluorophenyl, 2-bromophenyl, 2-chlorophenyl, 3-chlorophenyl,    4-chlorophenyl, 2,4-dichlorophenyl, 2,6-dichlorophenyl,    3,4-dichlorophenyl, 3,5-dichlorophenyl, 2,4,6-trichlorophenyl,    2,4,6-trifluorophenyl, 2-methoxyphenyl, 4-methoxyphenyl,    2,4-dimethoxyphenyl, 2,6-dimethoxyphenyl, 2-methylphenyl,    3-methylphenyl, 4-methylphenyl, 4-nitrophenyl,    2-(trifluoromethyl)phenyl, 3-(trifluoromethyl)phenyl,    4-(trifluoromethyl)phenyl, 2-(trifluoromethoxy)phenyl,    4-(trifluoromethoxy)phenyl, 4-tert-butylphenyl, biphenyl-2-yl,    biphenyl-3-yl, biphenyl-4-yl, 3-phenoxyphenyl, 4-phenoxyphenyl,    2-[1-methoxy-2-(methylamino)-2-oxoethyl]phenyl,    2-[(methylamino)(oxo)acetyl]phenyl 1-naphthyl, 2-naphthyl,    phenylethynyl, 2-thienyl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl,    quinolin-5-yl, quinolin-6-yl, quinolin-7-yl, quinolin-8-yl,    isoquinolin-5-yl, 1,3-benzoxazol-4-yl, trifluoromethyl,    morpholin-4-yl, piperidin-1-yl, pyrrolidin-1-yl,    4-methylpiperazin-1-yl, dimethylamino or trimethylsilyl, and the    agrochemically active salts thereof.

Most preference is given to compounds of the formula (I) in which one ormore of the symbols have one of the meanings below:

-   R¹ is methyl, ethyl, 1-methylethyl, 1,1-dimethylethyl,    difluoromethyl, trifluoromethyl or pentafluoroethyl,-   R² is H or chlorine,-   R³ is H, methyl, 1,1-dimethylethyl, difluoromethyl, trifluoromethyl,    pentafluoroethyl or phenyl,-   R⁴ is H or methyl,-   R⁵ is H or methyl,-   Y¹ is oxygen,-   Y² is oxygen,-   Y³ is sulfur or oxygen,-   X is CH₂ or CH₂CH₂,-   W is CH₂ or CH₂CH₂,-   R⁶ is H,-   G is a direct bond, CH₂, CH₂CH₂, CH(CH₃) or CH(CH₂CH₃),-   R⁷ is heptan-3-yl, octyl, (1Z)-prop-1-en-1-yl, (E)-2-phenylethenyl,    hex-1-en-3-yl, diphenylmethyl, 1,2,3,4-tetrahydronaphthalen-1-yl,    (1R)-1,2,3,4-tetrahydronaphthalen-1-yl,    (1S)-1,2,3,4-tetrahydronaphthalen-1-yl,    1,2,3,4-tetrahydronaphthalen-2-yl,    5,6,7,8-tetrahydronaphthalen-1-yl,    5,6,7,8-tetrahydronaphthalen-2-yl, decahydronaphthalen-1-yl,    1,4-dioxaspiro[4.5]dec-8-yl, 2,3-dihydro-1H-inden-1-yl,    2,3-dihydro-1H-inden-2-yl, cyclopropyl, cyclopentyl,    1-ethynylcyclopentyl, cyclohexyl, 2-methylcyclohexyl,    2,6-dimethylcyclohexyl, 4-tert-butylcyclohexyl,    5-methyl-2-(propan-2-yl)cyclohexyl,    3-methyl-5-(propan-2-yl)cyclohexyl, 1-cyanocyclohexyl,    1-ethynylcyclohexyl, cycloheptyl, cyclopropyl(phenyl)methyl,    (1S,2R)-1,7,7-trimethylbicyclo[2.2.1]hept-2-yl, phenyl,    2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl,    2,6-dichlorophenyl, 3,4-dichlorophenyl, 3,5-dichlorophenyl,    2,4,6-trichlorophenyl, 2,4,6-trifluorophenyl, 2-methoxyphenyl,    4-methoxyphenyl, 2,4-dimethoxyphenyl, 2,6-dimethoxyphenyl,    2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-nitrophenyl,    2-(trifluoromethyl)phenyl, 3-(trifluoromethyl)phenyl,    4-(trifluoromethyl)phenyl, 2-(trifluoromethoxy)phenyl,    4-(trifluoromethoxy)phenyl, 4-tert-butylphenyl, biphenyl-2-yl,    biphenyl-3-yl, biphenyl-4-yl, 3-phenoxyphenyl, 4-phenoxyphenyl,    1-naphthyl, 2-naphthyl, phenylethynyl, 2-thienyl, pyridin-2-yl,    pyridin-3-yl, pyridin-4-yl, quinolin-5-yl, quinolin-6-yl,    quinolin-7-yl, quinolin-8-yl, isoquinolin-5-yl, 1,3-benzoxazol-4-yl,    trifluoromethyl, dimethylamino or trimethylsilyl,    and the agrochemically active salts thereof.

Special preference is furthermore given to compounds of the formula (I)in which one or more of the symbols have one of the meanings below:

-   R¹ is C₁-C₄-alkyl or C₁-C₂-haloalkyl,-   R² is H and-   R³ is C₁-C₄-alkyl or C₁-C₂-haloalkyl,    where the other substituents have one or more of the meanings    mentioned above,    and the agrochemically active salts thereof.

Special preference is furthermore given to compounds of the formula (I)in which one or more of the symbols have one of the meanings below:

-   R¹ is methyl, ethyl, 1-methylethyl, 1,1-dimethylethyl,    difluoromethyl, trifluoromethyl or pentafluoroethyl,-   R² is H and-   R³ is methyl, 1,1-dimethylethyl, difluoromethyl, trifluoromethyl,    pentafluoroethyl or phenyl,    where the other substituents have one or more of the meanings    mentioned above, and the agrochemically active salts thereof.

Special preference is furthermore given to compounds of the formula (I)in which one or more of the symbols have one of the meanings below:

-   X is CH₂CH₂ and-   W is CH₂,    where the other substituents have one or more of the meanings    mentioned above, and the agrochemically active salts thereof.

Special preference is furthermore given to compounds of the formula (I)in which

-   Y³ is oxygen,    where the other substituents have one or more of the meanings    mentioned above, and the agrochemically active salts thereof.

Special preference is furthermore given to compounds of the formula (I)in which

-   R⁶ is H,    where the other substituents have one or more of the meanings    mentioned above, and the agrochemically active salts thereof.

Special preference is furthermore given to compounds of the formula (I)in which

-   G is CH₂, CH₂CH₂, CH(CH₃) or CH(CH₂CH₃),    where the other substituents have one or more of the meanings    mentioned above, and the agrochemically active salts thereof.

Special preference is furthermore given to compounds of the formula (I)in which

-   R⁷ is C₅-C₁₀-alkyl,    where the other substituents have one or more of the meanings    mentioned above, and the agrochemically active salts thereof.

Special preference is furthermore given to compounds of the formula (I)in which

-   R⁷ is C₅-C₈-alkyl,    where the other substituents have one or more of the meanings    mentioned above, and the agrochemically active salts thereof.

Very particular preference is furthermore given to compounds of theformula (I) in which

-   R⁷ is heptan-3-yl or octyl,    where the other substituents have one or more of the meanings    mentioned above, and the agrochemically active salts thereof.

Special preference is furthermore given to compounds of the formula (I)in which

-   R⁷ is C₂-C₁₆-alkenyl,    where the other substituents have one or more of the meanings    mentioned above, and the agrochemically active salts thereof.

Special preference is furthermore given to compounds of the formula (I)in which

-   R⁷ is C₂-C₆-alkenyl,    where the other substituents have one or more of the meanings    mentioned above, and the agrochemically active salts thereof.

Special preference is furthermore given to compounds of the formula (I)in which

-   R⁷ is (1Z)-prop-1-en-1-yl or hex-1-en-3-yl,    where the other substituents have one or more of the meanings    mentioned above, and the agrochemically active salts thereof.

Special preference is furthermore given to compounds of the formula (I)in which

-   R⁷ is C₂-C₁₆-alkynyl,    where the other substituents have one or more of the meanings    mentioned above, and the agrochemically active salts thereof.

Special preference is furthermore given to compounds of the formula (I)in which

-   R⁷ is C₂-C₆-alkynyl,    where the other substituents have one or more of the meanings    mentioned above, and the agrochemically active salts thereof.

Special preference is furthermore given to compounds of the formula (I)in which

-   R⁷ is C₃-C₁₅-cycloalkyl,    where the other substituents have one or more of the meanings    mentioned above, and the agrochemically active salts thereof.

Special preference is furthermore given to compounds of the formula (I)in which

-   R⁷ is C₃-C₈-cycloalkyl,    where the other substituents have one or more of the meanings    mentioned above, and the agrochemically active salts thereof.

Special preference is furthermore given to compounds of the formula (I)in which

-   R⁷ is cyclopropyl, cyclopentyl, cyclohexyl or cycloheptyl,    where the other substituents have one or more of the meanings    mentioned above, and the agrochemically active salts thereof.

Special preference is furthermore given to compounds of the formula (I)in which

-   R⁷ is C₅-C₁₅-cycloalkenyl,    where the other substituents have one or more of the meanings    mentioned above, and the agrochemically active salts thereof.

Special preference is furthermore given to compounds of the formula (I)in which

-   R⁷ is C₅-C₈-cycloalkenyl,    where the other substituents have one or more of the meanings    mentioned above, and the agrochemically active salts thereof.

Special preference is furthermore given to compounds of the formula (I)in which

-   R⁷ is C₃-C₁₅-heterocyclyl,    where the other substituents have one or more of the meanings    mentioned above, and the agrochemically active salts thereof.

Special preference is furthermore given to compounds of the formula (I)in which

-   R⁷ is C₅-C₆-heterocyclyl,    where the other substituents have one or more of the meanings    mentioned above, and the agrochemically active salts thereof.

Special preference is furthermore given to compounds of the formula (I)in which

-   R⁷ is aryl,    where the other substituents have one or more of the meanings    mentioned above, and the agrochemically active salts thereof.

Special preference is furthermore given to compounds of the formula (I)in which

-   R⁷ is phenyl, or saturated or partially or fully unsaturated    unsubstituted or substituted naphthyl or indenyl,    where the other substituents have one or more of the meanings    mentioned above, and the agrochemically active salts thereof.

Special preference is furthermore given to compounds of the formula (I)in which

-   R⁷ is phenyl, 1-naphthyl, 2-naphthyl,    1,2,3,4-tetrahydronaphthalen-1-yl,    (1R)-1,2,3,4-tetrahydronaphthalen-1-yl,    (1S)-1,2,3,4-tetrahydronaphthalen-1-yl,    1,2,3,4-tetrahydronaphthalen-2-yl,    5,6,7,8-tetrahydronaphthalen-1-yl,    5,6,7,8-tetrahydronaphthalen-2-yl, decahydronaphthalen-1-yl,    2,3-dihydro-1H-inden-1-yl or 2,3-dihydro-1H-inden-2-yl,    where the other substituents have one or more of the meanings    mentioned above, and the agrochemically active salts thereof.

Special preference is furthermore given to compounds of the formula (I)in which

-   R⁷ is hetaryl,    where the other substituents have one or more of the meanings    mentioned above, and the agrochemically active salts thereof.

Special preference is furthermore given to compounds of the formula (I)in which

-   R⁷ is furan-2-yl, furan-3-yl, thiophen-2-yl, thiophen-3-yl,    isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, pyrrol-1-yl,    pyrrol-2-yl, pyrrol-3-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl,    thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl,    isothiazol-4-yl, isothiazol-5-yl, pyrazol-1-yl, pyrazol-3-yl,    pyrazol-4-yl, imidazol-1-yl, imidazol-2-yl, imidazol-4-yl,    1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-oxadiazol-2-yl,    1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,3,4-thiadiazol-2-yl,    1,2,3-triazol-1-yl, 1,2,3-triazol-2-yl, 1,2,3-triazol-4-yl,    1,2,4-triazol-1-yl, 1,2,4-triazol-3-yl, 1,2,4-triazol-4-yl,    pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl,    pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl,    pyrazin-2-yl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl, indol-1-yl,    indol-2-yl, indol-3-yl, indol-4-yl, indol-5-yl, indol-6-yl,    indol-7-yl, benzimidazol-1-yl, benzimidazol-2-yl, benzimidazol-4-yl,    benzimidazol-5-yl, indazol-1-yl, indazol-3-yl, indazol-4-yl,    indazol-5-yl, indazol-6-yl, indazol-7-yl, indazol-2-yl,    1-benzofuran-2-yl, 1-benzofuran-3-yl, 1-benzofuran-4-yl,    1-benzofuran-5-yl, 1-benzofuran-6-yl, 1-benzofuran-7-yl,    1-benzothiophen-2-yl, 1-benzothiophen-3-yl, 1-benzothiophen-4-yl,    1-benzothiophen-5-yl, 1-benzothiophen-6-yl, 1-benzothiophen-7-yl,    1,3-benzothiazol-2-yl, 1,3-benzothiazol-4-yl, 1,3-benzothiazol-5-yl,    1,3-benzothiazol-6-yl, 1,3-benzothiazol-7-yl, 1,3-benzoxazol-2-yl,    1,3-benzoxazol-4-yl, 1,3-benzoxazol-5-yl, 1,3-benzoxazol-6-yl,    1,3-benzoxazol-7-yl, quinolin-2-yl, quinolin-3-yl, quinolin-4-yl,    quinolin-5-yl, quinolin-6-yl, quinolin-7-yl, quinolin-8-yl,    isoquinolin-1-yl, isoquinolin-3-yl, isoquinolin-4-yl,    isoquinolin-5-yl, isoquinolin-6-yl, isoquinolin-7-yl or    isoquinolin-8-yl,    where the other substituents have one or more of the meanings    mentioned above, and the agrochemically active salts thereof.

Special preference is furthermore given to compounds of the formula (I)in which

-   R⁷ is pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, quinolin-5-yl,    quinolin-6-yl, quinolin-7-yl, quinolin-8-yl, isoquinolin-5-yl or    1,3-benzoxazol-4-yl,    where the other substituents have one or more of the meanings    mentioned above, and the agrochemically active salts thereof.

Special preference is furthermore given to compounds of the formula (I)in which

-   R⁷ is Si(C₁-C₄-alkyl)₃,    where the other substituents have one or more of the meanings    mentioned above, and the agrochemically active salts thereof.

Special preference is furthermore given to compounds of the formula (I)in which

-   R⁷ is Si(C₁-C₂-alkyl)₃,    where the other substituents have one or more of the meanings    mentioned above, and the agrochemically active salts thereof.

Special preference is furthermore given to compounds of the formula (I)in which

-   R⁷ is trimethylsilyl,    where the other substituents have one or more of the meanings    mentioned above, and the agrochemically active salts thereof.

Depending on the nature of the substituents defined above, the compoundsof the formula (I) have acidic or basic properties and can form salts,if appropriate also inner salts, or adducts with inorganic or organicacids or with bases or with metal ions. If the compounds of the formula(I) carry amino, alkylamino or other groups which induce basicproperties, these compounds can be reacted with acids to give salts, orthey are directly obtained as salts in the synthesis. If the compoundsof the formula (I) carry hydroxyl, carboxyl or other groups which induceacidic properties, these compounds can be reacted with bases to givesalts. Suitable bases are, for example, hydroxides, carbonates,bicarbonates of the alkali metals and alkaline earth metals, inparticular those of sodium, potassium, magnesium and calcium,furthermore ammonia, primary, secondary and tertiary amines having(C₁-C₄)-alkyl groups, mono-, di- and trialkanolamines of(C₁-C₄)-alkanols, choline and also chlorocholine.

The salts obtainable in this manner also have fungicidal properties.

Examples of inorganic acids are hydrohalic acids, such as hydrogenfluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide,sulphuric acid, phosphoric acid and nitric acid, and acidic salts, suchas NaHSO₄ and KHSO₄. Suitable organic acids are, for example, formicacid, carbonic acid and alkanoic acids, such as acetic acid,trifluoroacetic acid, trichloroacetic acid and propionic acid, and alsoglycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid,benzoic acid, cinnamic acid, oxalic acid, alkylsulphonic acids(sulphonic acids having straight-chain or branched alkyl radicals of 1to 20 carbon atoms), arylsulphonic acids or aryldisulphonic acids(aromatic radicals, such as phenyl and naphthyl, which carry one or twosulphonic acid groups), alkylphosphonic acids (phosphonic acids havingstraight-chain or branched alkyl radicals of 1 to 20 carbon atoms),arylphosphonic acids or aryldiphosphonic acids (aromatic radicals, suchas phenyl and naphthyl, which carry one or two phosphonic acidradicals), where the alkyl and aryl radicals may carry furthersubstituents, for example p-toluenesulphonic acid, salicylic acid,p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid,etc.

Suitable metal ions are in particular the ions of the elements of thesecond main group, in particular calcium and magnesium, of the third andfourth main group, in particular aluminum, tin and lead, and also of thefirst to eighth transition group, in particular chromium, manganese,iron, cobalt, nickel, copper, zinc and others. Particular preference isgiven to the metal ions of the elements of the fourth period. Here, themetals can be present in various valencies that they can assume.

Optionally substituted groups can be mono- or polysubstituted, where inthe case of polysubstitutions the substituents can be identical ordifferent.

In the definitions of the symbols given in the formulae above,collective terms were used which are generally representative of thefollowing substituents:

halogen: fluorine, chlorine, bromine and iodine;aryl: unsubstituted or optionally substituted 5- to 15-memberedpartially or fully unsaturated mono-, bi- or tricyclic ring systemhaving up to 3 ring members selected from the groups C(═O), (C═S), whereat least one of the rings of the ring system is fully unsaturated, suchas, for example (but not limited to), benzene, naphthalene,tetrahydronaphthalene, anthracene, indane, phenanthrene, azulene;alkyl: saturated, straight-chain or branched hydrocarbon radicals having1 to 10 carbon atoms, for example (but not limited thereto) methyl,ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl,1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl,2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl,1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl,4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl,2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl, heptyl,1-methylhexyl, octyl, 1,1-dimethylhexyl, 2-ethylhexyl, 1-ethylhexyl,nonyl, 1,2,2-trimethylhexyl, decyl;haloalkyl: straight-chain or branched alkyl groups having 1 to 4 carbonatoms (as mentioned above), where in these groups some or all of thehydrogen atoms may be replaced by halogen atoms as mentioned above, forexample (but not limited thereto) C₁-C₂-haloalkyl, such aschloro-methyl, bromomethyl, dichloromethyl, trichloromethyl,fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl,dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl,1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl,2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl,2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl and1,1,1-trifluoroprop-2-yl;alkenyl: unsaturated, straight-chain or branched hydrocarbon radicalshaving 2 to 16 carbon atoms and at least one double bond in anyposition, for example (but not limited thereto) C₂-C₆-alkenyl, such asethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl,3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl,1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl,3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl,3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl,3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl,3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl,1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl,1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl,1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl,4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl,3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl,2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl,1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl,4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl,1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl,1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl,2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl,2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl,1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl,2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl,1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl,1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl;alkynyl: straight-chain or branched hydrocarbon groups having 2 to 16carbon atoms and at least one triple bond in any position, for example(but not limited thereto) C₂-C₆-alkynyl, such as ethynyl, 1-propynyl,2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl,1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl,1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl,1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl,3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl,1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl,2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl,4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl,1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl,3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl,2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl;alkoxy: saturated, straight-chain or branched alkoxy radicals having 1to 4 carbon atoms, for example (but not limited thereto) C₁-C₄-alkoxy,such as methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy,1-methylpropoxy, 2-methylpropoxy, 1,1-dimethylethoxy;haloalkoxy: straight-chain or branched alkoxy groups having 1 to 4carbon atoms (as mentioned above), where in these groups some or all ofthe hydrogen atoms may be replaced by halogen atoms as mentioned above,for example (but not limited thereto) C₁-C₂-haloalkoxy, such aschloro-methoxy, bromomethoxy, dichloromethoxy, trichloromethoxy,fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy,dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy,1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy,2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy,2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy,2,2,2-trichloroethoxy, pentafluoroethoxy and 1,1,1-trifluoroprop-2-oxy;thioalkyl: saturated, straight-chain or branched alkylthio radicalshaving 1 to 6 carbon atoms, for example (but not limited thereto)C₁-C₆-alkylthio, such as methylthio, ethylthio, propylthio,1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio,1,1-dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methylbutylthio,3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio,1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio,2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio,1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio,2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio,1-ethylbutylthio, 2-ethylbutylthio, 1,1,2-trimethylpropylthio,1,2,2-trimethyl-propylthio, 1-ethyl-1-methylpropylthio and1-ethyl-2-methylpropylthio;thiohaloalkyl: straight-chain or branched alkylthio groups having 1 to 6carbon atoms (as mentioned above), where in these groups some or all ofthe hydrogen atoms may be replaced by halogen atoms as mentioned above,for example (but not limited thereto) C₁-C₂-haloalkylthio, such aschloromethylthio, bromomethylthio, dichloromethylthio,trichloromethylthio, fluoromethylthio, difluoromethylthio,trifluoromethylthio, chlorofluoromethylthio, dichlorofluoromethylthio,chlorodifluoromethylthio, 1-chloroethylthio, 1-bromoethylthio,1-fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio,2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio,2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio,2,2,2-trichloroethylthio, pentafluoroethylthio and1,1,1-trifluoroprop-2-ylthio;cycloalkyl: mono-, bi- or tricyclic saturated hydrocarbon groups having3 to 12 carbon ring members, for example (but not limited thereto)cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl,bicyclo[1.0.1]butane, decalinyl, norbornyl;cycloalkenyl: mono-, bi- or tricyclic non-aromatic hydrocarbon groupshaving 5 to 15 carbon ring members and at least one double bond, forexample (but not limited thereto) cyclopenten-1-yl, cyclohexen-1-yl,cyclohepta-1,3-dien-1-yl, norbornen-1-yl;(alkoxy)carbonyl: an alkoxy group having 1 to 4 carbon atoms (asmentioned above) which is attached to the skeleton via a carbonyl group(—CO—);heterocyclyl: a three- to fifteen-membered saturated or partiallyunsaturated heterocycle which contains one to four heteroatoms from thegroup consisting of oxygen, nitrogen and sulfur: mono-, bi- or tricyclicheterocycles which contain, in addition to carbon ring members, one tothree nitrogen atoms and/or one oxygen or sulphur atom or one or twooxygen and/or sulphur atoms; if the ring contains a plurality of oxygenatoms, these are not directly adjacent; such as, for example (but notlimited thereto), oxiranyl, aziridinyl, 2-tetrahydrofuranyl,3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl,2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl,5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl,5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl,2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl,4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl,1,2,4-oxadiazolidin-3-yl, 1,2,4-oxadiazolidin-5-yl,1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl,1,2,4-triazolidin-3-yl, 1,3,4-oxadiazolidin-2-yl,1,3,4-thiadiazolidin-2-yl, 1,3,4-triazolidin-2-yl, 2,3-dihydrofur-2-yl,2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl,2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,4-dihydrothien-2-yl,2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl,3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl, 3-isoxazolin-3-yl,4-isoxazolin-3-yl, 2-isoxazolin-4-yl, 3-isoxazolin-4-yl,4-isoxazolin-4-yl, 2-isoxazolin-5-yl, 3-isoxazolin-5-yl,4-isoxazolin-5-yl, 2-isothiazolin-3-yl, 3-isothiazolin-3-yl,4-isothiazolin-3-yl, 2-isothiazolin-4-yl, 3-isothiazolin-4-yl,4-isothiazolin-4-yl, 2-isothiazolin-5-yl, 3-isothiazolin-5-yl,4-isothiazolin-5-yl, 2,3-dihydropyrazol-1-yl, 2,3-dihydropyrazol-2-yl,2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl,2,3-dihydropyrazol-5-yl, 3,4-dihydropyrazol-1-yl,3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl,3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-1-yl,4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl,4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl,2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl,3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 3,4-dihydrooxazol-5-yl,3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl,2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1,3-dioxan-5-yl,2-tetra-hydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothienyl,3-hexahydropyridazinyl, 4-hexahy-dropyridazinyl, 2-hexahydropyrimidinyl,4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl, 2-piperazinyl,1,3,5-hexahydrotriazin-2-yl and 1,2,4-hexahydrotriazin-3-yl;hetaryl: an unsubstituted or optionally substituted 5- to 15-memberedpartially or fully unsaturated mono-, bi- or tricyclic ring system whereat least one of the rings of the ring system is fully unsaturated andwhich contains one to four heteroatoms from the group consisting ofoxygen, nitrogen and sulfur; if the ring contains a plurality of oxygenatoms, these are not directly adjacent;such as, for example (but not limited thereto)

-   -   5-membered heteroaryl which contains one to four nitrogen atoms        or one to three nitrogen atoms and one sulfur or oxygen atom:        5-membered heteroaryl groups which, in addition to carbon atoms,        may contain one to four nitrogen atoms or one to three nitrogen        thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl,        4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl,        5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl,        2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl,        5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazol-3-yl,        1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl,        1,2,4-thiadia-zol-5-yl, 1,2,4-triazol-3-yl,        1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl and        1,3,4-triazol-2-yl;    -   benzo-fused 5-membered heteroaryl which contains one to three        nitrogen atoms or one nitrogen atom and one oxygen or sulfur        atom: 5-membered heteroaryl groups which, in addition to carbon        atoms, may contain one to four nitrogen atoms or one to three        nitrogen atoms and one sulfur or oxygen atom as ring members and        in which two adjacent carbon ring members or one nitrogen and        one adjacent carbon ring member may be bridged by a        buta-1,3-diene-1,4-diyl group in which one or two carbon atoms        may be replaced by nitrogen atoms; for example benzindolyl,        benzimidazolyl, benzothiazolyl, benzopyrazolyl, benzofuryl;    -   5-membered heteroaryl which contains one to four nitrogen atoms        and is attached via nitrogen or benzo-fused 5-membered        heteroaryl which contains one to three nitrogen atoms and is        attached via nitrogen: 5-membered heteroaryl groups which, in        addition to carbon atoms, may contain one to four nitrogen atoms        or one to three nitrogen atoms as ring members and in which two        adjacent carbon ring members or one nitrogen and one adjacent        carbon ring member may be bridged by a buta-1,3-diene-1,4-diyl        group in which one or two carbon atoms may be replaced by        nitrogen atoms, where these rings are attached to the skeleton        via one of the nitrogen ring members, for example 1-pyrrolyl,        1-pyrazolyl, 1,2,4-triazol-1-yl, 1-imidazolyl,        1,2,3-triazol-1-yl, 1,3,4-triazol-1-yl;    -   6-membered heteroaryl which contains one to three or one to four        nitrogen atoms: 6-membered heteroaryl groups which, in addition        to carbon atoms, may contain, respectively, one to three and one        to four nitrogen atoms as ring members, for example 2-pyridinyl,        3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl,        2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl,        1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl;

Not included are combinations which are against natural laws and whichthe person skilled in the art would therefore exclude based on his/herexpert knowledge. Ring structures having three or more adjacent oxygenatoms, for example, are excluded.

The present invention furthermore provides a process for preparing thethiazole-4-carboxylic esters and thioesters of the formula (I) accordingto the invention, which comprises at least one of steps (a) to (e)below:

-   (a) the conversion of a compound of the formula (VII) or (IX) into a    compound of the formula (VI) or (X), optionally in each case in the    presence of a solvent and, if appropriate, in the presence of an    acid or, if appropriate, in the presence of a base or, if    appropriate, in the presence of a hydrogen source, according to the    reaction scheme below (Scheme 1):

-   -   where    -   L=—O—C₁-C₂-alkyl for compounds of the formulae (VII) and (VI),    -   L=—Y³-G-R⁷ for compounds of the formulae (IX) and (X),    -   PG=acetyl, C₁-C₄-alkoxycarbonyl, benzyl or benzyloxycarbonyl,    -   W, X and R⁶ are as defined above for formula (I).

-   (b) the reaction of a compound of the formula (VI) or (X) with a    compound of the formula (V) to give a compound of the formula (IV)    or (I), in each case, if appropriate, in the presence of a coupling    agent, a base and a solvent, according to the reaction scheme below    (Scheme 2):

-   -   where    -   Z=Cl or OH,    -   L=—O—C₁-C₂-alkyl for compounds of the formulae (VI) and (IV),    -   L=—Y³-G-R⁷ for compounds of the formulae (X) and (I),    -   W, X, Y³, G, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are as defined above        for formula (I).

-   (c) the conversion of a compound of the formula (IV) or (VII) into a    compound of the formula (III) or (VIII), in each case by hydrolysis    in the presence of a base and, if appropriate, in the presence of a    solvent, according to the reaction scheme below (Scheme 3):

-   -   where

for compounds of the formulae (IV) and (III),

-   -   Q=acetyl, C₁-C₄-alkoxycarbonyl, benzyl or benzyloxycarbonyl        (corresponds to PG), for compounds of the formulae (VII) and        (VIII),    -   W, X, R¹, R², R³, R⁴, R⁵ and R⁶ are as defined above for formula        (I).

-   (d) the reaction of a compound of the formula (III) or (VIII) with a    compound of the formula (II) to give a compound of the formula (I)    or (IX), in each case, if appropriate, in the presence of a coupling    agent, a base and a solvent, according to the reaction scheme below    (Scheme 4):

-   -   where

for compounds of the formulae (III) and (I),

-   -   Q=acetyl, C₁-C₄-alkoxycarbonyl, benzyl or benzyloxycarbonyl        (corresponds to PG), for compounds of the formulae (VIII) and        (IX),    -   Z═OH or chlorine,    -   W, X, Y³, G, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are as defined above        for formula (I).

-   (e) the conversion of a compound of the formula (I) into a compound    of the formula (I) in the presence of a sulfurizing agent and, if    appropriate, in the presence of a solvent, according to the reaction    scheme below (Scheme 5):

-   -   where    -   Y¹=sulfur or oxygen,    -   Y²=sulfur or oxygen,    -   W, X, Y³, G, R², R³, R⁴, R⁵, R⁶ and R⁷ are as defined above for        formula (I).

A general overview of the synthesis paths is given in Scheme 6.

The protective group is removed from compounds of the formula (VII),giving compounds of the formula (VI) or the corresponding salt (Scheme1). A compound of the formula (VI) or a corresponding salt is coupledwith a substrate of the formula (V), which gives compounds of theformula (IV) (Scheme 2). The hydrolysis of compounds of the formula (IV)leads to carboxylic acids of the formula (III) (Scheme 3), followed by acoupling reaction in the presence of an alcohol or thiol of the generalformula (II), which gives compounds of the formula (I) (Scheme 4).Alternatively, the hydrolysis of the compound of the formula (VII) leadsto a carboxylic acid of the general formula (VIII) (Scheme 3), followedby a coupling reaction in the presence of an alcohol or thiol of thegeneral formula (II), which gives a compound of the formula (IX) (Scheme4). The protective group marked PG of a compound of the formula (IX) isremoved, so that a compound of the formula (X) or the corresponding saltis formed (Scheme 1). A compound of the formula (X) or a correspondingsalt is coupled with a substrate of the formula (V), which gives acompound of the formula (I) (Scheme 2). A sulfurizing agent is added toa compound of the formula (I) to form a compound of the formula (I)(Y¹=sulfur or oxygen, Y²=sulfur or oxygen) (Scheme 5).

One way of preparing the intermediate (VI) from corresponding compounds(VII) is shown in Scheme 1.

A compound of the formula (VII) is converted into a compound of theformula (VI) using suitable methods for removing protective groups,which methods are described in the literature (“Protective Groups inOrganic Synthesis”; Third Edition; Theodora W. Greene, Peter G. M. Wuts;494-653, and the literature cited therein).

tert-Butoxycarbonyl and benzyloxycarbonyl protective groups can beremoved in an acidic medium (for example using hydrochloric acid ortrifluoroacetic acid). Acetyl protective groups can be removed underbasic conditions (using, for example, potassium carbonate or cesiumcarbonate). Benzylic protective groups can be removed hydrogenolyticallyusing hydrogen in the presence of a catalyst (for example palladium onactivated carbon).

Suitable for use as solvents are all customary solvents which are inertunder the reaction conditions, such as, for example, alcohols (forexample methanol, ethanol, propanol), cyclic and acyclic ethers (forexample diethyl ether, tetrahydrofuran, dioxane), aromatic hydrocarbons(for example benzene, toluene, xylene), halogenated hydrocarbons (forexample dichloromethane, chloroform, carbon tetrachloride), halogenatedaromatic hydrocarbons (for example chlorobenzene, dichlorobenzene),nitriles (for example acetonitrile), carboxylic esters (for exampleethyl acetate), amides (for example N,N-dimethylformamide,N,N-dimethylacetamide), dimethyl sulfoxide,1,3-dimethyl-2-imidazolinone, water and acetic acid, or the reaction canbe carried out in mixtures of two or more of these solvents.

Acids which can be used for this reaction of deprotectingt-butoxycarbonyl and benzyloxycarbonyl groups are, for example,trifluoroacetic acid, hydrochloric acid or other acids, as described inthe literature (for example “Protective Groups in Organic Synthesis”;Third Edition; Theodora W. Greene, Peter G. M. Wuts; pp. 494-653).

The reaction is usually carried out at temperatures of 0° C.-150° C. andpreferably at room temperature, but it can also be carried out at thereflux temperature of the reaction mixture. The reaction time variesdepending on the scale of the reaction and the reaction temperature, butis generally between half an hour and 72 hours.

After the reaction has ended, the compounds (VI) are removed from thereaction mixture using one of the customary separation techniques. Ifrequired, the compounds are purified by recrystallisation, distillationor chromatography, or they can, if appropriate, also be used for thenext step without prior purification. Moreover, it is possible toisolate the compound of the general formula (VI) as a salt, for exampleas a salt of hydrochloric acid or trifluoroacetic acid.

The same process is used to convert a compound of the formula (IX) intoa compound of the formula (X).

C₁-C₂-Alkyl esters (VII) are known and can be prepared from commerciallyavailable precursors according to procedures described in theliterature, for example from nitriles of the formula (XI), carboxylicacids of the formula (XII), carbonyl chlorides of the formula (XIII),amides of the formula (XIV) or thioamides of the formula (XV) (FIG. 1).A preferred method is the Hantzsch thiazole synthesis. Starting with(XIV) and commercially available ethyl or methyl halpyruvate in ethanolor in N,N-dimethylformamide in the presence of, for example,triethylamine at room temperature (for examples see WO 07/014,290 andthe references cited therein).

-   -   where    -   Q=H or acid-labile amine protective groups, such as, for        example, t-butoxycarbonyl (tBoc) or benzyloxycarbonyl (Cbz), or        a benzyl protective group, such as, for example, benzyl (Bn).    -   W and X are as defined above for formula (I).

One way of preparing compounds of the formula (IV) from correspondingcompounds (VI) is shown in Scheme 2.

A compound of the formula (IV) is synthesized by a coupling reaction ofa compound of the formula (VI) with a substrate of the formula (V) whereZ═Cl, if appropriate in the presence of an acid scavenger/a base.

Acid halides (V) (Z═Cl) or the corresponding carboxylic acids (V) (Z═OH)are commercially available or can be prepared by processes described inthe literature (for examples see WO 07/014,290 and the references citedtherein). A preferred method is shown in Scheme 7. Pyrazoles (XVIII) canbe prepared from diketones (XXI) and commercially available hydrazine(XX) or the corresponding HCl salt in ethanol or inN,N-dimethylformamide, if appropriate in the presence of bases, forexample triethylamine at reflux. Compounds (XVI) can be prepared byalkylation of compounds (XVIII) with commercially available α-haloesters (XVII) in acetonitrile or in N,N-dimethylformamide in thepresence of bases, for example potassium carbonate at room temperature.Alternatively, compounds (XVI) can be prepared directly from diketones(XXI) and commercially available hydrazine (XIX) or the correspondingHCl salts in ethanol or in N,N-dimethylformamide, if appropriate in thepresence of bases, for example triethylamine at reflux. Carboxylic acids(V) (Z═OH) can be prepared by hydrolysis of the esters (XVI) inTHF/water mixtures using lithium hydroxide at room temperature.Moreover, a substrate of the general formula (V) where Z═Cl can beprepared from the corresponding acid (Z═OH) by chlorination usingprocesses known from the literature (for example Tetrahedron 2005, 61,10827-10852, and the literature cited therein).

Suitable for use as solvents are all customary solvents which are inertunder the reaction conditions, such as, for example, alcohols (forexample methanol, ethanol, propanol), cyclic and acyclic ethers (forexample diethyl ether, tetrahydrofuran, dioxane), aromatic hydrocarbons(for example benzene, toluene, xylene), halogenated hydrocarbons (forexample dichloromethane, chloroform, carbon tetrachloride), halogenatedaromatic hydrocarbons (for example chlorobenzene, dichlorobenzene) andnitriles (for example acetonitrile), or the reaction can be carried outin mixtures of two or more of these solvents. The preferred solvents aretetrahydrofuran and dichloromethane.

At least one equivalent of an acid scavenger/a base (for example Hünigbase, triethylamine or commercially available polymeric acidscavengers), based on the starting material of the general formula (V),is employed. If the starting material is a salt, at least twoequivalents of the acid scavenger are required.

The reaction is usually carried out at temperatures of 0° C.-100° C. andpreferably at 20° C.-30° C., but it can also be carried out at thereflux temperature of the reaction mixture. The reaction time variesdepending on the scale of the reaction and the reaction temperature, butis generally between a few minutes and 48 hours.

After the reaction has ended, the compounds (IV) are removed from thereaction mixture using one of the customary separation techniques. Ifrequired, the compounds are purified by recrystallisation, distillationor chromatography, or they can, if appropriate, also be used for thenext step without prior purification.

Alternatively, a compound of the formula (IV) can also be synthesizedfrom the corresponding compound of the formula (VI) using a substrate ofthe formula (V) where Z═OH in the presence of a coupling agentanalogously to procedures described in the literature (for exampleTetrahedron 2005, 61, 10827-10852, and the references cited therein).

Suitable coupling agents are, for example, peptide coupling agents (forexample N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide mixed with4-dimethylaminopyridine, N-(3-dimethylaminopropyl)-N′-ethylcarbodiimidemixed with 1-hydroxybenzotriazole, bromotripyrrolidinophosphoniumhexafluorophosphate,O-(7-azabenzotriazol-1-yl)-N,N,N′,N′-tetramethyluroniumhexafluorophosphate, etc.).

If appropriate, a base, such as, for example, triethylamine or Hünigbase can be employed in the reaction.

Suitable for use as solvents are all customary solvents which are inertunder the reaction conditions, such as, for example, alcohols (forexample methanol, ethanol, propanol), cyclic and acyclic ethers (forexample diethyl ether, tetrahydrofuran, dioxane), aromatic hydrocarbons(for example benzene, toluene, xylene), halogenated hydrocarbons (forexample dichloromethane, chloroform, carbon tetrachloride), halogenatedaromatic hydrocarbons (for example chlorobenzene, dichlorobenzene),nitriles (for example acetonitrile) and amides (for exampleN,N-dimethylformamide, N,N-dimethylacetamide), or the reaction can becarried out in mixtures of two or more of these solvents. The preferredsolvent is dichloromethane.

The reaction is usually carried out at temperatures of 0° C.-100° C. andpreferably at 0° C.-30° C., but it can also be carried out at the refluxtemperature of the reaction mixture. The reaction time varies dependingon the scale of the reaction and the reaction temperature, but isgenerally between a few minutes and 48 hours.

After the reaction has ended, the compounds (IV) are removed from thereaction mixture using one of the customary separation techniques. Ifrequired, the compounds are purified by recrystallisation, distillationor chromatography, or they can, if appropriate, also be used for thenext step without prior purification.

Analogously, it is possible to convert compounds of the formula (X) intocompounds of the formula (I).

One way of preparing the intermediate (III) from corresponding compounds(IV) is shown in Scheme 3.

The carboxylic acid of the formula (III) can be prepared by hydrolysisof the corresponding C₁-C₂-alkyl ester of the formula (IV). It ispossible to use, for example, the method described in WO2007/014290.

Suitable for use as solvents are all customary solvents which are inertunder the reaction conditions, such as, for example, alcohols (forexample methanol, ethanol, propanol), cyclic and acyclic ethers (forexample diethyl ether, tetrahydrofuran, dioxane), aromatic hydrocarbons(for example benzene, toluene, xylene), halogenated hydrocarbons (forexample dichloromethane, chloroform, carbon tetrachloride) andhalogenated aromatic hydrocarbons (for example chlorobenzene,dichlorobenzene), or the reaction can be carried out in mixtures of twoor more of these solvents.

Suitable alkali metal hydroxides are, for example, LiOH, NaOH or KOH,usually in the presence of water together with a cosolvent, preferablyTHF and/or methanol, to facilitate dissolution of the ester. Thestarting material and the alkali metal hydroxide are employed inequimolar amounts; however, the alkali metal hydroxide may, if required,also be used in excess. The carboxylate salt formed is converted intothe free acid by treatment with a slight excess of mineral acids, suchas, for example, hydrochloric acid or sulfuric acid.

The reaction is usually carried out at temperatures of 0° C.-60° C., butit can also be carried out at the reflux temperature of the reactionmixture. The reaction time varies depending on the scale of the reactionand the reaction temperature, but is generally between a few minutes and48 hours.

After the reaction has ended, the compounds (III) are removed from thereaction mixture using one of the customary separation techniques. Ifrequired, the compounds are purified by recrystallisation, distillationor chromatography.

Analogously, it is possible to convert compounds of the formula (VII)into compounds of the formula (VIII).

One way of preparing compounds of the formula (I) from correspondingcompounds (III) is shown in Scheme 4.

A compound of the formula (I) is synthesized by a coupling reaction of acompound of the formula (III) with a substrate of the formula (II), bychlorination using processes known from the literature (for exampleTetrahedron 2005, 61, 10827-10852, and the literature cited therein), ifappropriate in the presence of an acid scavenger/a base.

Substrates of the general formula (II) are commercially available or canbe prepared by processes described in the literature (see, for example,“The Chemistry of Functional groups”; “The Chemistry of the ThiolGroup”; John Wiley & Sons, 1974, 163-269, and the references citedtherein).

Suitable for use as solvents are all customary solvents which are inertunder the reaction conditions, such as, for example, alcohols (forexample methanol, ethanol, propanol), cyclic and acyclic ethers (forexample diethyl ether, tetrahydrofuran, dioxane), aromatic hydrocarbons(for example benzene, toluene, xylene), halogenated hydrocarbons (forexample dichloromethane, chloroform, carbon tetrachloride), halogenatedaromatic hydrocarbons (for example chlorobenzene, dichlorobenzene) andnitriles (for example acetonitrile), or the reaction can be carried outin mixtures of two or more of these solvents. The preferred solvents aretetrahydrofuran and dichloromethane.

At least one equivalent of an acid scavenger/a base (for example Hünigbase, triethylamine or commercially available polymeric acidscavengers), based on the starting material of the general formula (II),is employed. If the starting material is a salt, at least twoequivalents of the acid scavenger are required.

The reaction is usually carried out at temperatures of 0° C.-100° C. andpreferably at 20° C.-30° C., but it can also be carried out at thereflux temperature of the reaction mixture. The reaction time variesdepending on the scale of the reaction and the reaction temperature, butis generally between a few minutes and 48 hours.

After the reaction has ended, the compounds (I) are removed from thereaction mixture using one of the customary separation techniques. Ifrequired, the compounds are purified by recrystallisation, distillationor chromatography, or they can, if appropriate, also be used for thenext step without prior purification.

Alternatively, a compound of the formula (I) can also be synthesizedfrom the corresponding compound of the formula (III) (Z═OH) using asubstrate of the formula (II) in the presence of a coupling agentanalogously to procedures described in the literature (for exampleTetrahedron 2005, 61, 10827-10852, and the references cited therein).

Suitable coupling agents are, for example, peptide coupling agents (forexample N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide mixed with4-dimethylaminopyridine, N-(3-dimethylaminopropyl)-N′-ethylcarbodiimidemixed with 1-hydroxybenzotriazole, bromotripyrrolidinophosphoniumhexafluorophosphate,O-(7-azabenzotriazol-1-yl)-N,N,N′,N′-tetramethyluroniumhexafluorophosphate, etc.).

If appropriate, a base, such as, for example, triethylamine or Hünigbase can be employed in the reaction.

Suitable for use as solvents are all customary solvents which are inertunder the reaction conditions, such as, for example, alcohols (forexample methanol, ethanol, propanol), cyclic and acyclic ethers (forexample diethyl ether, tetrahydrofuran, dioxane), aromatic hydrocarbons(for example benzene, toluene, xylene), halogenated hydrocarbons (forexample dichloromethane, chloroform, carbon tetrachloride), halogenatedaromatic hydrocarbons (for example chlorobenzene, dichlorobenzene),nitriles (for example acetonitrile) and amides (for exampleN,N-dimethylformamide, N,N-dimethylacetamide), or the reaction can becarried out in mixtures of two or more of these solvents. The preferredsolvents are N,N-dimethylformiamide and dichloromethane.

The reaction is usually carried out at temperatures of 0° C.-100° C. andpreferably at 0° C.-30° C., but it can also be carried out at the refluxtemperature of the reaction mixture. The reaction time varies dependingon the scale of the reaction and the reaction temperature, but isgenerally between a few minutes and 48 hours.

After the reaction has ended, the compounds (I) are removed from thereaction mixture using one of the customary separation techniques. Ifrequired, the compounds are purified by recrystallisation, distillationor chromatography, or they can, if appropriate, also be used for thenext step without prior purification.

The same process can be used to convert a compound of the generalformula (VIII) into a compound of the general formula (IX).

One way to prepare compounds of the formula (I) in which Y′ and Y²═Sfrom corresponding compounds (I) in which Y′ and Y²═O is shown in Scheme5.

A sulfurizing agent, such as, for example, Lawesson's reagent or, forexample, phosphorus pentasulfide, is added to a compound of the formula(I) to form a compound of the formula (I) (Y′ and Y²=sulfur). Here, itis possible, for example, to use the method described in TetrahedronLett 2002, 43 (3), 371-373.

Suitable for use as solvents are all customary solvents which are inertunder the reaction conditions, such as, for example, alcohols (forexample methanol, ethanol, propanol), cyclic and acyclic ethers (forexample diethyl ether, tetrahydrofuran, dioxane), aromatic hydrocarbons(for example benzene, toluene, xylene), halogenated hydrocarbons (forexample dichloromethane, chloroform, carbon tetrachloride), halogenatedaromatic hydrocarbons (for example chlorobenzene, dichlorobenzene),nitriles (for example acetonitrile), carboxylic esters (for exampleethyl acetate) and amides (for example N,N-dimethylformamide,N,N-dimethylacetamide), and the reaction can be carried out in mixturesof two or more of these solvents. The preferred solvents are chloroform,toluene and 1,2-dimethoxyethane.

Suitable sulfurizing agents are, for example, Lawesson's reagent (seeTetrahedron 1986, 42, 6555-6564, Tetrahedron Lett. 1993, 46, 7459-7462)and phosphorus pentasulfide. The starting material and the sulfurizingagent are employed in equimolar amounts; however, the sulfurizing agentmay, if required, also be used in excess.

The reaction is usually carried out at temperatures of 0° C.-150° C. andpreferably at 0° C.-100° C., but it can also be carried out at thereflux temperature of the reaction mixture. The reaction time variesdepending on the scale of the reaction and the reaction temperature, butis generally between a few minutes and 48 hours.

After the reaction has ended, the compounds (I) are removed from thereaction mixture using one of the customary separation techniques. Ifrequired, the compounds are purified by recrystallisation, distillationor chromatography.

The compound of the formula (XVIII-1)

and salts thereof are novel.

The compounds of the formulae (XVI-1), (XVI-2), (XVI-3), (XVI-4) and(XVI-5),

and salts thereof are novel.

The compounds of the formulae (V-1), (V-2), (V-3), (V-4) and (V-5),

and salts thereof are novel.

The compounds of the formulae (IV-1), (IV-2) and (IV-3),

and salts thereof are novel.

The compounds of the formulae (III-1), (III-2) and (III-3) in which

-   Z═OH or chlorine    and salts thereof are novel.

The compounds of the formula (IX) in which

the symbols have the meanings below

-   PG is acetyl, C₁-C₂-alkoxycarbonyl, benzyl or benzyloxycarbonyl,-   W, X, Y³, G, R⁶ and R⁷ have the general, preferred, particularly    preferred or very particularly preferred meanings given above    and salts thereof are novel.

The compounds of the formula (X) in which

the symbols have the meanings below

-   W, X, Y³, G, R⁶ and R⁷ have the general, preferred, particularly    preferred or very particularly preferred meanings given above    and salts thereof are novel.

The invention furthermore provides the non-medicinal use of thethiazole-4-carboxylic esters and thioesters according to the inventionor mixtures thereof for controlling unwanted microorganisms.

The invention furthermore relates to a composition for controllingunwanted microorganisms which comprises at least onethiazole-4-carboxylic ester or thioester according to the presentinvention.

Moreover, the invention relates to a method for controlling unwantedmicroorganisms, characterized in that the thiazole-4-carboxylic estersand thioesters according to the invention are applied to themicroorganisms and/or in their habitat.

The invention furthermore relates to seed treated with at least onethiazole-4-carboxylic ester or thioester according to the invention.

A last subject matter of the invention relates to a method forprotecting seed against unwanted microorganisms by using seed treatedwith at least one thiazole-4-carboxylic ester or thioester according tothe present invention.

The substances according to the invention have potent microbicidalactivity and can be employed for controlling unwanted microorganisms,such as fungi and bacteria, in crop protection and in the protection ofmaterials.

The thiazole-4-carboxylic esters and thioesters of the formula (I)according to the invention have very good fungicidal properties and canbe used in crop protection, for example, for controllingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

Bactericides can be employed in crop protection, for example, forcontrolling Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae,Corynebacteriaceae and Streptomycetaceae.

The fungicidal compositions according to the invention can be used forthe curative or protective control of phytopathogenic fungi.Accordingly, the invention also relates to curative and protectivemethods for controlling phytopathogenic fungi using the active compoundsor compositions according to the invention, which are applied to theseed, the plant or plant parts, the fruit or the soil in which theplants grow.

The compositions according to the invention for controllingphytopathogenic fungi in crop protection comprise an effective, butnon-phytotoxic amount of the active compounds according to theinvention. “Effective, but non-phytotoxic amount” means an amount of thecomposition according to the invention which is sufficient to controlthe fungal disease of the plant in a satisfactory manner or to eradicatethe fungal disease completely, and which, at the same time, does notcause any significant symptoms of phytotoxicity. In general, thisapplication rate may vary within a relatively wide range. It depends ona plurality of factors, for example on the fungus to be controlled, theplant, the climatic conditions and the ingredients of the compositionsaccording to the invention.

All plants and plant parts can be treated in accordance with theinvention. By plants are understood here all plants and plantpopulations such as desired and undesired wild plants or crop plants(including naturally occurring crop plants). Crop plants can be plantswhich can be obtained by conventional breeding and optimization methodsor by biotechnological and genetic engineering methods or combinationsof these methods, including the transgenic plants and including theplant varieties which can or cannot be protected by varietal propertyrights. Plant parts are to be understood as meaning all parts and organsof plants above and below the ground, such as shoot, leaf, flower androot, examples which may be mentioned being leaves, needles, stalks,stems, flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes.Parts of plants also include harvested plants and vegetative andgenerative propagation material, for example seedlings, tubers,rhizomes, cuttings and seeds.

The following plants may be mentioned as plants which can be treatedaccording to the invention: cotton, flax, grapevines, fruit, vegetables,such as Rosaceae sp. (for example pomaceous fruit, such as apples andpears, but also stone fruit, such as apricots, cherries, almonds andpeaches and soft fruit such as strawberries), Ribesioidae sp.,Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp.,Moraceae sp., Oleaceae sp., Actimidaceae sp., Lauraceae sp., Musaceaesp. (for example banana trees and plantations), Rubiaceae sp. (forexample coffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (forexample lemons, oranges and grapefruit), Solanaceae sp. (for exampletomatoes), Liliaceae sp., Asteraceae sp. (for example lettuce),Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp.(for example cucumbers), Alliaceae sp. (for example leek, onions),Papilionaceae sp. (for example peas); major crop plants, such asGramineae sp. (for example maize, lawn, cereals such as wheat, rye,rice, barley, oats, millet and triticale), Asteraceae sp. (for examplesunflowers), Brassicaceae sp. (for example white cabbage, red cabbage,broccoli, cauliflowers, brussels sprouts, pak Choi, kohlrabi, gardenradish, and also oilseed rape, mustard, horseradish and cress), Fabacaesp. (for example beans, peanuts), Papilionaceae sp. (for example soyabeans), Solanaceae sp. (for example potatoes), Chenopodiaceae sp. (forexample sugarbeet, fodderbeet, swiss chard, beetroot); crop plants andornamental plants in garden and forest; and also in each casegenetically modified varieties of these plants. Preference is given totreating cereal plants according to the invention.

Some pathogens of fungal diseases which can be treated according to theinvention may be mentioned by way of example, but not by way oflimitation:

diseases caused by powdery mildew pathogens, such as, for example,Blumeria species, such as, for example, Blumeria graminis; Podosphaeraspecies, such as, for example, Podosphaera leuco-tricha; Sphaerothecaspecies, such as, for example, Sphaerotheca fuliginea; Uncinula species,such as, for example, Uncinula necator;diseases caused by rust disease pathogens, such as, for example,Gymnosporangium species, such as, for example, Gymnosporangium sabinae;Hemileia species, such as, for example, Hemileia vastatrix; Phakopsoraspecies, such as, for example, Phakopsora pachyrhizi and Phakopsorameibomiae; Puccinia species, such as, for example, Puccinia recondita orPuccinia triticina; Uromyces species, such as, for example, Uromycesappendiculatus;diseases caused by pathogens from the group of the Oomycetes, such as,for example, Bremia species, such as, for example, Bremia lactucae;Peronospora species, such as, for example, Peronospora pisi or P.brassicae; Phytophthora species, such as, for example, Phytophthorainfestans; Plasmopara species, such as, for example, Plasmoparaviticola; Pseudoperonospora species, such as, for example,Pseudoperonospora humuli or Pseudoperonospora cubensis; Pythium species,such as, for example, Pythium ultimum;leaf blotch diseases and leaf wilt diseases caused, for example, byAlternaria species, such as, for example, Alternaria solani; Cercosporaspecies, such as, for example, Cercospora beticola; Cladiosporiumspecies, such as, for example, Cladiosporium cucumerinum; Cochliobolusspecies, such as, for example, Cochliobolus sativus (conidia form:Drechslera, syn: Helminthosporium); Colletotrichum species, such as, forexample, Colletotrichum lindemuthanium; Cycloconium species, such as,for example, Cycloconium oleaginum; Diaporthe species, such as, forexample, Diaporthe citri; Elsinoe species, such as, for example, Elsinoefawcettii; Gloeosporium species, such as, for example, Gloeosporiumlaeticolor; Glomerella species, such as, for example, Glomerellacingulata; Guignardia species, such as, for example, Guignardiabidwelli; Leptosphaeria species, such as, for example, Leptosphaeriamaculans; Magnaporthe species, such as, for example, Magnaporthe grisea;Microdochium species, such as, for example, Microdochium nivale;Mycosphaerella species, such as, for example, Mycosphaerella graminicolaand M. fijiensis; Phaeosphaeria species, such as, for example,Phaeosphaeria nodorum; Pyrenophora species, such as, for example,Pyrenophora teres; Ramularia species, such as, for example, Ramulariacollocygni; Rhynchosporium species, such as, for example, Rhynchosporiumsecalis; Septoria species, such as, for example, Septoria apii; Typhulaspecies, such as, for example, Typhula incamata; Venturia species, suchas, for example, Venturia inaequalis;root and stem diseases caused, for example, by Corticium species, suchas, for example, Corticium graminearum; Fusarium species, such as, forexample, Fusarium oxysporum; Gaeumannomyces species, such as, forexample, Gaeumannomyces graminis; Rhizoctonia species, such as, forexample Rhizoctonia solani; Tapesia species, such as, for example,Tapesia acuformis; Thielaviopsis species, such as, for example,Thielaviopsis basicola;ear and panicle diseases (including corn cobs) caused, for example, byAlternaria species, such as, for example, Alternaria spp.; Aspergillusspecies, such as, for example, Aspergillus flavus; Cladosporium species,such as, for example, Cladosporium cladosporioides; Claviceps species,such as, for example, Claviceps purpurea; Fusarium species, such as, forexample, Fusarium culmorum; Gibberella species, such as, for example,Gibberella zeae; Monographella species, such as, for example,Monographella nivalis; Septoria species, such as, for example, Septorianodorum;diseases caused by smut fungi, such as, for example, Sphacelothecaspecies, such as, for example, Sphacelotheca reiliana; Tilletia species,such as, for example, Tilletia caries, T. controversa; Urocystisspecies, such as, for example, Urocystis occulta; Ustilago species, suchas, for example, Ustilago nuda, U. nuda tritici;Fruit rot caused, for example, by Aspergillus species, such as, forexample, Aspergillus flavus; Botrytis species, such as, for example,Botrytis cinerea; Penicillium species, such as, for example, Penicilliumexpansum and P. purpurogenum; Sclerotinia species, such as, for example,Sclerotinia sclerotiorum;Verticilium species, such as, for example, Verticilium alboatrum;seed- and soil-borne rot and wilt diseases, and also diseases ofseedlings, caused, for example, by Fusarium species, such as, forexample, Fusarium culmorum; Phytophthora species, such as, for example,Phytophthora cactorum; Pythium species, such as, for example, Pythiumultimum; Rhizoctonia species, such as, for example, Rhizoctonia solani;Sclerotium species, such as, for example, Sclerotium rolfsii;cancerous diseases, galls and witches' broom caused, for example, byNectria species, such as, for example, Nectria galligena;wilt diseases caused, for example, by Monilinia species, such as, forexample, Monilinia laxa;deformations of leaves, flowers and fruits caused, for example, byTaphrina species, such as, for example, Taphrina deformans;degenerative diseases of woody plants caused, for example, by Escaspecies, such as, for example, Phaeomoniella chlamydospora andPhaeoacremonium aleophilum and Fomitiporia mediterranea;diseases of flowers and seeds caused, for example, by Botrytis species,such as, for example, Botrytis cinerea;diseases of plant tubers caused, for example, by Rhizoctonia species,such as, for example, Rhizoctonia solani; Helminthosporium species, suchas, for example, Helminthosporium solani;diseases caused by bacterial pathogens, such as, for example,Xanthomonas species, such as, for example, Xanthomonas campestris pv.oryzae; Pseudomonas species, such as, for example, Pseudomonas syringaepv. lachrymans; Erwinia species, such as, for example, Erwiniaamylovora;

Preference is given to controlling the following diseases of soybeans:

Fungal diseases on leaves, stems, pods and seeds caused, for example, byalternaria leaf spot (Alternaria spec. atrans tenuissima), anthracnose(Colletotrichum gloeosporoides dematium var. truncatum), brown spot(Septoria glycines), cercospora leaf spot and blight (Cercosporakikuchii), choanephora leaf blight (Choanephora infundibulifera trispora(Syn.)), dactuliophora leaf spot (Dactuliophora glycines), downy mildew(Peronospora manshurica), drechslera blight (Drechslera glycini),frogeye leaf spot (Cercospora sojina), leptosphaerulina leaf spot(Leptosphaerulina trifolii), phyllostica leaf spot (Phyllostictasojaecola), pod and stem blight (Phomopsis sojae), powdery mildew(Microsphaera diffusa), pyrenochaeta leaf spot (Pyrenochaeta glycines),rhizoctonia aerial, foliage, and web blight (Rhizoctonia solani), rust(Phakopsora pachyrhizi Phakopsora meibomiae), scab (Sphacelomaglycines), stemphylium leaf blight (Stemphylium botryosum), target spot(Corynespora cassiicola).Fungal diseases on roots and the stem base caused, for example, by blackroot rot (Calonectria crotalariae), charcoal rot (Macrophominaphaseolina), fusarium blight or wilt, root rot, and pod and collar rot(Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusariumequiseti), mycoleptodiscus root rot (Mycoleptodiscus terrestris),neocosmospora (Neocosmospora vasinfecta), pod and stem blight (Diaporthephaseolorum), stem canker (Diaporthe phaseolorum var. caulivora),phytophthora rot (Phytophthora megasperma), brown stem rot (Phialophoragregata), pythium rot (Pythium aphanideunatum, Pythium irregulare,Pythium debaryanum, Pythium myriotylum, Pythium ultimum), rhizoctoniaroot rot, stem decay, and damping-off (Rhizoctonia solani), sclerotiniastem decay (Sclerotinia sclerotiorum), sclerotinia southern blight(Sclerotinia rolfsii), thielaviopsis root rot (Thielaviopsis basicola).

The active compounds according to the invention also have very goodfortifying action in plants. Accordingly, they can be used formobilizing the defenses of the plant against attack by undesirablemicroorganisms.

Plant-strengthening (resistance-inducing) substances are to beunderstood as meaning, in the present context, those substances whichare capable of stimulating the defense system of plants in such a waythat the treated plants, when subsequently inoculated with undesiredmicroorganisms, develop a high degree of resistance to thesemicroorganisms.

In the present case, undesirable microorganisms are to be understood asmeaning phytopathogenic fungi and bacteria. Accordingly, the substancesaccording to the invention can be used to protect plants for a certainperiod after the treatment against attack by the pathogens mentioned.The period for which protection is provided generally extends over 1 to10 days, preferably 1 to 7 days, after the treatment of the plants withthe active compounds.

The fact that the active compounds are well tolerated by plants at theconcentrations required for controlling plant diseases permits thetreatment of above-ground parts of plants, of propagation stock andseeds, and of the soil.

The active compounds according to the invention can be employedparticularly successfully for controlling diseases in viticulture andfruit and vegetable growing such as, for example, against Botrytis,Venturia, Sphaerotheca, Podosphaera, Phythophthora and Plasmoparaspecies.

The active compounds according to the invention are also suitable forincreasing the yield of crops. In addition, they show reduced toxicityand are well tolerated by plants.

If appropriate, the compounds according to the invention can, at certainconcentrations or application rates, also be used as herbicides,safeners, growth regulators or agents to improve plant properties, or asmicrobicides, for example as fungicides, antimycotics, bactericides,viricides (including agents against viroids) or as agents against MLO(Mycoplasma-like organisms) and RLO (Rickettsia-like organisms). Ifappropriate, they can also be used as intermediates or precursors forthe synthesis of other active compounds.

If appropriate, the active compounds according to the invention can alsobe employed in specific concentrations and application rates asherbicides, for influencing plant growth, and for controlling animalpests. If appropriate, they can also be used as intermediates andprecursors for the synthesis of further active compounds.

The active compounds according to the invention, in combination withgood plant tolerance and favourable toxicity to warm-blooded animals andbeing tolerated well by the environment, are suitable for protectingplants and plant organs, for increasing the harvest yields, forimproving the quality of the harvested material and for controllinganimal pests, in particular insects, arachnids, helminths, nematodes andmolluscs, which are encountered in agriculture, in horticulture, inanimal husbandry, in forests, in gardens and leisure facilities, in theprotection of stored products and of materials, and in the hygienesector. They may be preferably employed as plant protection agents.

The treatment according to the invention of the plants and plant partswith the active compounds or compositions is carried out directly or byaction on their surroundings, habitat or storage space using customarytreatment methods, for example by dipping, spraying, atomizing,irrigating, evaporating, dusting, fogging, broadcasting, foaming,painting, spreading-on, watering (drenching), drip irrigating and, inthe case of propagation material, in particular in the case of seeds,furthermore as a powder for dry seed treatment, a solution for seedtreatment, a water-soluble powder for slurry treatment, by incrusting,by coating with one or more coats, etc. It is furthermore possible toapply the active compounds by the ultra-low volume method or to injectthe active compound preparation or the active compound itself into thesoil.

The active compounds according to the invention can also be used asdefoliants, desiccants, haulm killers and, especially, as weedkillers.Weeds in the broadest sense are understood to mean all plants which growin locations where they are undesired. Whether the substances accordingto the invention act as total or selective herbicides dependsessentially on the amount used.

Moreover, in the protection of materials, the active compounds orcompositions according to the invention can be employed for protectingindustrial materials against attack and destruction by unwantedmicroorganisms, such as, for example, fungi.

Industrial materials in the present context are understood as meaningnon-living materials which have been prepared for use in industry. Forexample, industrial materials which are intended to be protected byactive compounds according to the invention from microbial change ordestruction can be adhesives, sizes, paper and board, textiles, leather,wood, paints and plastic articles, cooling lubricants and othermaterials which can be infected with, or destroyed by, microorganisms.Parts of production plants, for example cooling-water circuits, whichmay be impaired by the proliferation of microorganisms may also bementioned within the scope of the materials to be protected. Industrialmaterials which may be mentioned within the scope of the presentinvention are preferably adhesives, sizes, paper and board, leather,wood, paints, cooling lubricants and heat-transfer liquids particularlypreferably wood. The active compounds or compositions according to theinvention may prevent disadvantageous effects, such as rotting, decay,discoloration, decoloration or formation of mold.

The method according to the invention for controlling unwanted fungi canalso be employed for protecting storage goods. Here, storage goods areto be understood as meaning natural substances of vegetable or animalorigin or processed products thereof of natural origin, for whichlong-term protection is desired. Storage goods of vegetable origin, suchas, for example, plants or plant parts, such as stems, leaves, tubers,seeds, fruits, grains, can be protected freshly harvested or afterprocessing by (pre)drying, moistening, comminuting, grinding, pressingor roasting. Storage goods also include timber, both unprocessed, suchas construction timber, electricity poles and barriers, or in the formof finished products, such as furniture. Storage goods of animal originare, for example, hides, leather, furs and hairs. The active compoundsaccording to the invention may prevent disadvantageous effects, such asrotting, decay, discoloration, decoloration or formation of mold.

Microorganisms capable of degrading or changing the industrial materialswhich may be mentioned are, for example, bacteria, fungi, yeasts, algaeand slime organisms. The active compounds according to the inventionpreferably act against fungi, in particular molds, wood-discoloring andwood-destroying fungi (Basidiomycetes), and against slime organisms andalgae. Microorganisms of the following genera may be mentioned asexamples: Alternaria, such as Alternaria tenuis; Aspergillus, such asAspergillus niger; Chaetomium, such as Chaetomium globosum; Coniophora,such as Coniophora puetana; Lentinus, such as Lentinus tigrinus;Penicillium, such as Penicillium glaucum; Polyporus, such as Polyporusversicolor; Aureobasidium, such as Aureobasidium pullulans; Sclerophoma,such as Sclerophoma pityophila; Trichoderma, such as Trichoderma viride;Escherichia, such as Escherichia coli; Pseudomonas, such as Pseudomonasaeruginosa; Staphylococcus, such as Staphylococcus aureus.

The present invention furthermore relates to a composition forcontrolling unwanted microorganisms, which composition comprises atleast one of the thiazole-4-carboxylic ester or thioesters according tothe invention. These are preferably fungicidal composition whichcomprise agriculturally suitable auxiliaries, solvents, carriers,surfactants or extenders.

According to the invention, a carrier is a natural or synthetic organicor inorganic substance with which the active compounds are mixed orbonded for better applicability, in particular for application to plantsor plant parts or seed. The carrier, which may be solid or liquid, isgenerally inert and should be suitable for use in agriculture.

As solid carriers these are suitable: for example ammonium salts andground natural minerals such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticmaterials such as highly-disperse silica, alumina and silicates;suitable solid carriers for granules are: for example, crushed andfractionated natural rocks such as calcite, marble, pumice, sepioliteand dolomite, and also synthetic granules of inorganic and organicmeals, and granules of organic material such as paper, sawdust, coconutshells, maize cobs and tobacco stalks; suitable emulsifiers and/orfoam-formers are: for example, nonionic and anionic emulsifiers, such aspolyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers,for example alkylaryl polyglycol ethers, alkylsulfonates, alkylsulphates, arylsulfonates and also protein hydrolysates; suitabledispersants are nonionic and/or ionic substances, for example from theclasses of the alcohol-POE and/or —POP ethers, acid and/or POP POEesters, alkylaryl and/or POP POE ethers, fat and/or POP POE adducts,POE- and/or POP-polyol derivatives, POE- and/or POP-sorbitan or -sugaradducts, alkyl or aryl sulphates, alkyl- or arylsulphonates and alkyl oraryl phosphates or the corresponding PO-ether adducts. Furthermore,suitable oligo- or polymers, for example those derived from vinylicmonomers, from acrylic acid, from EO and/or PO alone or in combinationwith, for example, (poly)alcohols or (poly)amines. It is also possibleto employ lignin and its sulphonic acid derivatives, unmodified andmodified celluloses, aromatic and/or aliphatic sulphonic acids and theiradducts with formaldehyde.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, water- and oil-basedsuspensions, powders, dusts, pastes, soluble powders, soluble granules,granules for broadcasting, suspoemulsion concentrates, natural compoundsimpregnated with active compound, synthetic substances impregnated withactive compound, fertilizers and also microencapsulations in polymericsubstances.

The active compounds can be applied as such, in the form of theirformulations or the use forms prepared therefrom, such as ready-to-usesolutions, emulsions, water- or oil-based suspensions, powders, wettablepowders, pastes, soluble powders, dusts, soluble granules, granules forbroadcasting, suspoemulsion concentrates, natural products impregnatedwith active compound, synthetic materials impregnated with activecompound, fertilizers and also microencapsulations in polymericsubstances. Application is carried out in a customary manner, forexample by watering, spraying, atomizing, broadcasting, dusting,foaming, spreading, etc. It is furthermore possible to apply the activecompounds by the ultra-low volume method, or to inject the activecompound preparation or the active compound itself into the soil. It isalso possible to treat the seeds of the plants.

The formulations mentioned can be prepared in a manner known per se, forexample by mixing the active compounds with at least one customaryextender, solvent or diluent, emulsifier, dispersant, and/or binder orfixative, wetting agent, water-repellent, if appropriate desiccants andUV stabilizers and, if appropriate, dyes and pigments, defoamers,preservatives, secondary thickeners, adhesives, gibberellins and alsofurther processing auxiliaries.

The compositions according to the invention include not onlyformulations which are already ready for use and can be applied with asuitable apparatus to the plant or the seed, but also commercialconcentrates which have to be diluted with water prior to use.

The active compounds according to the invention can be present as suchor in their (commercial) formulations and in the use forms prepared fromthese formulations as a mixture with other (known) active compounds,such as insecticides, attractants, sterilants, bactericides, acaricides,nematicides, fungicides, growth regulators, herbicides, fertilizers,safeners and/or semiochemicals.

Suitable for use as auxiliaries are substances which are suitable forimparting to the composition itself and/or to preparations derivedtherefrom (for example spray liquors, seed dressings) particularproperties such as certain technical properties and/or also particularbiological properties. Typical suitable auxiliaries are: extenders,solvents and carriers.

Suitable extenders are, for example, water, polar and nonpolar organicchemical liquids, for example from the classes of the aromatic andnon-aromatic hydrocarbons (such as paraffins, alkylbenzenes,alkylnaphthalenes, chlorobenzenes), the alcohols and polyols (which, ifappropriate, may also be substituted, etherified and/or esterified), theketones (such as acetone, cyclohexanone), esters (including fats andoils) and (poly)ethers, the unsubstituted and substituted amines,amides, lactams (such as N-alkylpyrrolidones) and lactones, thesulphones and sulphoxides (such as dimethyl sulphoxide).

Liquefied gaseous extenders or carriers are to be understood as meaningliquids which are gaseous at standard temperature and under atmosphericpressure, for example aerosol propellants such as halogenatedhydrocarbons, or else butane, propane, nitrogen and carbon dioxide.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, or else naturalphospholipids such as cephalins and lecithins and syntheticphospholipids can be used in the formulations. Other possible additivesare mineral and vegetable oils.

If the extender used is water, it is also possible to employ, forexample, organic solvents as auxiliary solvents. Essentially, suitableliquid solvents are: aromatics such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics or chlorinated aliphatichydrocarbons such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons such as cyclohexane or paraffins, forexample petroleum fractions, alcohols such as butanol or glycol andtheir ethers and esters, ketones such as acetone, methyl ethyl ketone,methyl isobutyl ketone or cyclohexanone, strongly polar solvents such asdimethylformamide or dimethyl sulphoxide, or else water.

The compositions according to the invention may comprise additionalfurther components, such as, for example, surfactants. Suitablesurfactants are emulsifiers and/or foam formers, dispersants or wettingagents having ionic or nonionic properties, or mixtures of thesesurfactants. Examples of these are salts of polyacrylic acid, salts oflignosulphonic acid, salts of phenolsulphonic acid ornaphthalenesulphonic acid, polycondensates of ethylene oxide with fattyalcohols or with fatty acids or with fatty amines, substituted phenols(preferably alkylphenols or arylphenols), salts of sulphosuccinicesters, taurine derivatives (preferably alkyl taurates), phosphoricesters of polyethoxylated alcohols or phenols, fatty esters of polyols,and derivatives of the compounds containing sulphates, sulphonates andphosphates, for example alkylaryl polyglycol ethers, alkylsulphonates,alkyl sulphates, arylsulphonates, protein hydrolysates, lignosulphitewaste liquors and methylcellulose. The presence of a surfactant isrequired if one of the active compounds and/or one of the inert carriersis insoluble in water and when the application takes place in water. Theproportion of surfactants is between 5 and 40 percent by weight of thecomposition according to the invention.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs suchas alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs,and trace nutrients such as salts of iron, manganese, boron, copper,cobalt, molybdenum and zinc.

Other possible additives are perfumes, mineral or vegetable, optionallymodified oils, waxes and nutrients (including trace nutrients), such assalts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

Stabilizers, such as low-temperature stabilizers, preservatives,antioxidants, light stabilizers or other agents which improve chemicaland/or physical stability may also be present.

If appropriate, other additional components may also be present, forexample protective colloids, binders, adhesives, thickeners, thixotropicsubstances, penetrants, stabilizers, sequestering agents, complexformers. In general, the active compounds can be combined with any solidor liquid additive customarily used for formulation purposes.

The formulations generally comprise between 0.05 and 99% by weight, 0.01and 98% by weight, preferably between 0.1 and 95% by weight,particularly preferably between 0.5 and 90% of active compound, veryparticularly preferably between 10 and 70% by weight.

The formulations described above can be used in a method according tothe invention for controlling unwanted microorganisms, where thethiazole-4-carboxylic esters and thioesters according to the inventionare applied to the microorganisms and/or to their habitat.

The active compounds according to the invention can be used as such orin their formulations, also in a mixture with known fungicides,bactericides, acaricides, nematicides or insecticides, to broaden, forexample, the activity spectrum or to prevent development of resistance.

Suitable mixing partners are, for example, known fungicides,insecticides, acaricides, nematicides or else bactericides (see alsoPesticide Manual, 13th ed.).

A mixture with other known active compounds, such as herbicides, or withfertilizers and growth regulators, safeners and/or semiochemicals isalso possible.

The compounds are employed in a customary manner appropriate for the useforms.

The invention furthermore includes a method for treating seed.

A further aspect of the present invention relates in particular to seedtreated with at least one of the thiazole-4-carboxylic esters orthioesters according to the invention. The seed according to theinvention is used in methods for protecting seed against animal pestsand/or phytopathogenic harmful fungi. In these methods, seed treatedwith at least one active compound according to the invention isemployed.

The active compounds or compositions according to the invention are alsosuitable for treating seed. A large part of the damage to crop plantscaused by harmful organisms is triggered by the infection of the seedduring storage or after sowing both during and after germination of theplant. This phase is particularly critical since the roots and shoots ofthe growing plant are particularly sensitive, and even small damage mayresult in the death of the plant. Accordingly, there is great interestin protecting the seed and the germinating plant by using appropriatecompositions.

The control of animal pests and/or phytopathogenic harmful fungi bytreating the seed of plants has been known for a long time and is thesubject of continuous improvements. However, the treatment of seedentails a series of problems which cannot always be solved in asatisfactory manner. Thus, it is desirable to develop methods forprotecting the seed and the germinating plant which dispense with, or atleast reduce considerably, the additional application of crop protectionagents after planting or after emergence of the plants. It isfurthermore desirable to optimize the amount of active compound employedin such a way as to provide optimum protection for the seed and thegerminating plant from attack by phytopathogenic fungi, but withoutdamaging the plant itself by the active compound employed. Inparticular, methods for the treatment of seed should also take intoconsideration the intrinsic fungicidal properties of transgenic plantsin order to achieve optimum protection of the seed and the germinatingplant with a minimum of crop protection agents being employed.

Accordingly, the present invention also relates to a method forprotecting seed and germinating plants against attack by animal pestsand/or phytopathogenic harmful fungi by treating the seed with acomposition according to the invention. The invention also relates tothe use of the compositions according to the invention for treating seedfor protecting the seed and the germinating plant againstphytopathogenic fungi. Furthermore, the invention relates to seedtreated with a composition according to the invention for protectionagainst phytopathogenic fungi.

The control of animal pests and/or phytopathogenic harmful fungi whichdamage plants post-emergence is carried out primarily by treating thesoil and the above-ground parts of plants with plant protection agents.Owing to the concerns regarding a possible impact of the plantprotection agent on the environment and the health of humans andanimals, there are efforts to reduce the amount of active compoundsapplied.

One of the advantages of the present invention is that, because of theparticular systemic properties of the compositions according to theinvention, treatment of the seed with these compositions not onlyprotects the seed itself, but also the resulting plants after emergence,from animal pests and/or phytopathogenic harmful fungi. In this manner,the immediate treatment of the crop at the time of sowing or shortlythereafter can be dispensed with.

It is also considered to be advantageous that the active compounds orcompositions according to the invention can be used in particular alsofor transgenic seed where the plant growing from this seed is capable ofexpressing a protein which acts against pests. By treating such seedwith the active compounds or compositions according to the invention,even by the expression of the, for example, insecticidal protein,certain pests may be controlled. Surprisingly, a further synergisticeffect may be observed here, which additionally increases theeffectiveness of the protection against attack by pests.

The compositions according to the invention are suitable for protectingseed of any plant variety which is employed in agriculture, in thegreenhouse, in forests or in horticulture. In particular, this takes thefaun of seed of cereals (such as wheat, barley, rye, millet and oats),maize, cotton, soybeans, rice, potatoes, sunflowers, beans, coffee,beets (for example sugarbeets and fodder beets), peanuts, vegetables(such as such as tomatoes, cucumbers, onions and lettuce), lawn andornamental plants. The treatment of the seed of cereals (such as wheat,barley, rye and oats), maize and rice is of particular importance.

As also described further below, the treatment of transgenic seed withthe active compounds or compositions according to the invention is ofparticular importance. This refers to the seed of plants containing atleast one heterologous gene which allows the expression of a polypeptideor protein having insecticidal properties. The heterologous gene intransgenic seed can originate, for example, from microorganisms of thespecies Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma,Clavibacter, Glomus or Gliocladium. Preferably, this heterologous geneis from Bacillus sp., the gene product having activity against theEuropean corn borer and/or the Western corn rootworm. Particularlypreferably, the heterologous gene originates from Bacillusthuringiensis.

Within the context of the present invention, the composition accordingto the invention is applied to the seed either alone or in suitableformulation. Preferably, the seed is treated in a state in which it isstable enough to avoid damage during treatment. In general, the seed maybe treated at any point in time between harvest and sowing. The seedusually used has been separated from the plant and freed from cobs,shells, stalks, coats, hairs or the flesh of the fruits. Thus, it ispossible to use, for example, seed which has been harvested, cleaned anddried to a moisture content of less than 15% by weight. Alternatively,it is also possible to use seed which, after drying, has been treated,for example, with water and then dried again.

When treating the seed, care must generally be taken that the amount ofthe composition according to the invention applied to the seed and/orthe amount of further additives is chosen in such a way that thegermination of the seed is not adversely affected, or that the resultingplant is not damaged. This must be borne in mind in particular in thecase of active compounds which can have phytotoxic effects at certainapplication rates.

The compositions according to the invention can be applied directly,i.e. without any other components and undiluted. In general, it ispreferred to apply the compositions to the seed in the form of asuitable formulation. Suitable formulations and methods for treatingseed are known to the person skilled in the art and are described, forexample, in the following documents: U.S. Pat. No. 4,272,417 A, U.S.Pat. No. 4,245,432 A, U.S. Pat. No. 4,808,430 A, U.S. Pat. No. 5,876,739A, US 2003/0176428 A1, WO 2002/080675 A1, WO 2002/028186 A2.

The active compounds which can be used in accordance with the inventioncan be converted into the customary seed-dressing formulations, such assolutions, emulsions, suspensions, powders, foams, slurries or othercoating compositions for seed, and also ULV formulations

These formulations are prepared in a known manner, by mixing the activecompounds or active compound combinations with customary additives suchas, for example, customary extenders and also solvents or diluents,colorants, wetting agents, dispersants, emulsifiers, antifoams,preservatives, secondary thickeners, adhesives, gibberellins and alsowater.

Colorants which may be present in the seed-dressing formulations whichcan be used in accordance with the invention are all colorants which arecustomary for such purposes. In this context, not only pigments, whichare sparingly soluble in water, but also dyes, which are soluble inwater, may be used. Examples which may be mentioned are the colorantsknown by the names Rhodamin B, C.I. Pigment Red 112 and C.I. Solvent Red1.

Suitable wetting agents which may be present in the seed-dressingformulations which can be used in accordance with the invention are allsubstances which promote wetting and which are conventionally used forthe formulation of agrochemical active compounds. Preference is given tousing alkylnaphthalenesulphonates, such as diisopropyl- ordiisobutylnaphthalenesulphonates.

Suitable dispersants and/or emulsifiers which may be present in theseed-dressing formulations which can be used in accordance with theinvention are all nonionic, anionic and cationic dispersantsconventionally used for the formulation of agrochemical activecompounds. Preference is given to using nonionic or anionic dispersantsor mixtures of nonionic or anionic dispersants. Suitable nonionicdispersants which may be mentioned are, in particular, ethyleneoxide/propylene oxide block polymers, alkylphenol polyglycol ethers andtristryrylphenol polyglycol ether, and their phosphated or sulphatedderivatives. Suitable anionic dispersants are, in particular,lignosulphonates, polyacrylic acid salts and arylsulphonate/formaldehydecondensates.

Antifoams which may be present in the seed-dressing formulations whichcan be used in accordance with the invention are all foam-inhibitingsubstances conventionally used for the formulation of agrochemicalactive compounds. Silicone antifoams and magnesium stearate canpreferably be used.

Preservatives which may be present in the seed-dressing formulationswhich can be used in accordance with the invention are all substanceswhich can be employed for such purposes in agrochemical compositions.Dichlorophene and benzyl alcohol hemiformal may be mentioned by way ofexample.

Secondary thickeners which may be present in the seed-dressingformulations which can be used in accordance with the invention are allsubstances which can be employed for such purposes in agrochemicalcompositions. Cellulose derivatives, acrylic acid derivatives, xanthan,modified clays and finely divided silica are preferred.

Adhesives which may be present in the seed-dressing formulations whichcan be used in accordance with the invention are all customary binderswhich can be employed in seed-dressing products. Polyvinylpyrrolidone,polyvinyl acetate, polyvinyl alcohol and tylose may be mentioned asbeing preferred.

Gibberellins which can be present in the seed-dressing formulationswhich can be used in accordance with the invention are preferably thegibberellins A1, A3 (=gibberellic acid), A4 and A7; gibberellic acid isespecially preferably used. The gibberellins are known (cf. R. Wegler“Chemie der Pflanzenschutz- and Schädlingsbekämpfungsmittel” [Chemistryof plant protection agents and pesticides], vol. 2, Springer Verlag,1970, p. 401-412).

The seed-dressing formulations which can be used in accordance with theinvention can be employed for the treatment of a wide range of seed,either directly or after previously having been diluted with water.Thus, the concentrates or the preparations obtainable therefrom bydilution with water may be used to dress the seed of cereals, such aswheat, barley, rye, oats, and triticale, and also the seed of maize,rice, oilseed rape, peas, beans, cotton, sunflowers, and beets, or elsevegetable seed of any of a very wide variety of kinds. The seed-dressingformulations which can be used according to the invention or theirdilute preparations may also be used to dress seed of transgenic plants.In this context, additional synergistic effects may also occur incooperation with the substances formed by expression.

All mixers which can conventionally be employed for the seed-dressingoperation are suitable for treating seed with the seed-dressingformulations which can be used in accordance with the invention or withthe preparations prepared therefrom by addition of water. Specifically,a procedure is followed during the seed-dressing operation in which theseed is placed into a mixer, the specific desired amount ofseed-dressing formulations, either as such or after previously havingbeen diluted with water, is added, and everything is mixed until theformulation is distributed uniformly on the seed. If appropriate, thisis followed by a drying process.

The application rate of the seed dressing formulations which can be usedaccording to the invention may be varied within a relatively wide range.It depends on the respective content of the active compounds in theformulations and on the seed. The active compound combinationapplication rates are generally between 0.001 and 50 g per kilogram ofseed, preferably between 0.01 and 15 g per kilogram of seed.

In addition, the compounds of the formula (I) according to the inventionalso have very good antimycotic activity. They have a very broadantimycotic activity spectrum in particular against dermatophytes andyeasts, molds and diphasic fungi, (for example against Candida species,such as Candida albicans, Candida glabrata), and Epidermophytonfloccosum, Aspergillus species, such as Aspergillus niger andAspergillus fumigatus, Trichophyton species, such as Trichophytonmentagrophytes, Microsporon species such as Microsporon canis andaudouinii. The list of these fungi by no means limits the mycoticspectrum covered, but is only for illustration.

Accordingly, the active compounds of the formula (I) according to theinvention can be used both in medical and in non-medical applications.

The active compounds can be used as such, in the form of theirformulations or the use forms prepared therefrom, such as ready-to-usesolutions, suspensions, wettable powders, pastes, soluble powders, dustsand granules. Application is carried out in a customary manner, forexample by watering, spraying, atomizing, broadcasting, dusting,foaming, spreading, etc. It is furthermore possible to apply the activecompounds by the ultra-low volume method, or to inject the activecompound preparation or the active compound itself into the soil. It isalso possible to treat the seed of the plants.

When using the active compounds according to the invention asfungicides, the application rates can be varied within a relatively widerange, depending on the kind of application. The application rate of theactive compounds according to the invention is

-   -   when treating plant parts, for example leaves: from 0.1 to 10        000 g/ha, preferably from 10 to 1 000 g/ha, particularly        preferably from 50 to 300 g/ha (when the application is carried        out by watering or dripping, it is even possible to reduce the        application rate, especially when inert substrates such as rock        wool or perlite are used);    -   when treating seed: from 2 to 200 g per 100 kg of seed,        preferably from 3 to 150 g per 100 kg of seed, particularly        preferably from 2.5 to 25 g per 100 kg of seed, very        particularly preferably from 2.5 to 12.5 g per 100 kg of seed;    -   when treating the soil: from 0.1 to 10 000 g/ha, preferably from        1 to 5000 g/ha.

These application rates are mentioned only by way of example and are notlimiting in the sense of the invention.

With respect to possible additional partners for mixing, reference ismade to the insecticides and fungicides mentioned above.

The compounds according to the invention can at the same time beemployed for protecting objects which come into contact with saltwateror brackish water, such as hulls, screens, nets, buildings, moorings andsignaling systems, against fouling.

Furthermore, the compounds according to the invention can be used aloneor in combinations with other active compounds as antifoulingcompositions.

The method of treatment according to the invention can be used in thetreatment of genetically modified organisms (GMOs), e.g. plants orseeds. Genetically modified plants (or transgenic plants) are plants inwhich a heterologous gene has been stably integrated into the genome.The expression “heterologous gene” essentially means a gene which isprovided or assembled outside the plant and when introduced in thenuclear, chloroplastic or hypochondrial genome gives the transformedplant new or improved agronomic or other properties by expressing aprotein or polypeptide of interest or by downregulating or silencingother gene(s) which are present in the plant (using for exampleantisense technology, cosuppression technology or RNAi technology [RNAinterference]). A heterologous gene that is located in the genome isalso called a transgene. A transgene that is defined by its particularlocation in the plant genome is called a transformation or transgenicevent.

Depending on the plant species or plant varieties, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Possible are thus, for example, the followingeffects which exceed the effects which were to be expected: reducedapplication rates and/or a widening of the activity spectrum and/or anincrease in the activity of the active compounds and compositions whichcan be used according to the invention, better plant growth, increasedtolerance to high or low temperatures, increased tolerance to drought orto water or soil salt content, increased flowering performance, easierharvesting, accelerated maturation, higher harvest yields, biggerfruits, larger plant height, greener leaf color, earlier flowering,higher quality and/or a higher nutritional value of the harvestedproducts, higher sugar concentration within the fruits, better storagestability and/or processability of the harvested products.

At certain application rates, the active compound combinations accordingto the invention may also have a strengthening effect in plants.Accordingly, they are suitable for mobilizing the defense system of theplant against attack by unwanted phytopathogenic fungi and/ormicroorganisms and/or viruses. This may, if appropriate, be one of thereasons for the enhanced activity of the combinations according to theinvention, for example against fungi. Plant-strengthening(resistance-inducing) substances are to be understood as meaning, in thepresent context, also those substances or combinations of substanceswhich are capable of stimulating the defense system of plants in such away that, when subsequently inoculated with unwanted phytopathogenicfungi and/or microorganisms and/or viruses, the treated plants display asubstantial degree of resistance to these unwanted phytopathogenic fungiand/or microorganisms and/or viruses. In the present case, unwantedphytopathogenic fungi and/or microorganisms and/or viruses areunderstood as meaning phytopathogenic fungi, bacteria and viruses. Thus,the substances according to the invention can be employed for protectingplants against attack by the abovementioned pathogens within a certainperiod of time after the treatment. The period within which protectionis brought about generally extends from 1 to 10 days, preferably 1 to 7days, after the treatment of the plants with the active compounds.

Plants and plant varieties which are preferably treated according to theinvention include all plants which have genetic material which impartsparticularly advantageous, useful traits to these plants (whetherobtained by breeding and/or biotechnological means).

Plants and plant varieties which are also preferably treated accordingto the invention are resistant against one or more biotic stresses, i.e.said plants have a better defense against animal and microbial pests,such as against nematodes, insects, mites, phytopathogenic fungi,bacteria, viruses and/or viroids.

Plants and plant varieties which may also be treated according to theinvention are those plants which are resistant to one or more abioticstress factors. Abiotic stress conditions may include, for example,drought, cold temperature exposure, heat exposure, osmotic stress,waterlogging, increased soil salinity, increased exposure to minerals,exposure to ozone, exposure to strong light, limited availability ofnitrogen nutrients, limited availability of phosphorus nutrients orshade avoidance.

Plants and plant varieties which may also be treated according to theinvention are those plants characterized by enhanced yieldcharacteristics. Enhanced yield in said plants can be the result of, forexample, improved plant physiology, growth and development, such aswater use efficiency, water retention efficiency, improved nitrogen use,enhanced carbon assimilation, improved photosynthesis, increasedgermination efficiency and accelerated maturation. Yield can furthermorebe affected by improved plant architecture (under stress and non-stressconditions), including early flowering, flowering control for hybridseed production, seedling vigour, plant size, internode number anddistance, root growth, seed size, fruit size, pod size, pod or earnumber, seed number per pod or ear, seed mass, enhanced seed filling,reduced seed dispersal, reduced pod dehiscence and lodging resistance.Further yield traits include seed composition, such as carbohydratecontent, protein content, oil content and composition, nutritionalvalue, reduction in anti-nutritional compounds, improved processabilityand better storage stability.

Plants that may be treated according to the invention are hybrid plantsthat already express the characteristics of heterosis, or hybrid vigour,which results in generally higher yield, vigour, health and resistancetowards biotic and abiotic stress factors. Such plants are typicallymade by crossing an inbred male-sterile parent line (the female parent)with another inbred male-fertile parent line (the male parent). Hybridseed is typically harvested from the male sterile plants and sold togrowers. Male sterile plants can sometimes (e.g. in corn) be produced bydetasseling (i.e. the mechanical removal of the male reproductive organsor male flowers) but, more typically, male sterility is the result ofgenetic determinants in the plant genome. In that case, and especiallywhen seed is the desired product to be harvested from the hybrid plants,it is typically useful to ensure that male fertility in the hybridplants, which contain the genetic determinants responsible for malesterility, is fully restored. This can be accomplished by ensuring thatthe male parents have appropriate fertility restorer genes which arecapable of restoring the male fertility in hybrid plants that containthe genetic determinants responsible for male sterility. Geneticdeterminants for male sterility may be located in the cytoplasm.Examples of cytoplasmic male sterility (CMS) were for instance describedfor Brassica species. However, genetic determinants for male sterilitycan also be located in the nuclear genome. Male sterile plants can alsobe obtained by plant biotechnology methods such as genetic engineering.A particularly useful means of obtaining male sterile plants isdescribed in WO 89/10396 in which, for example, a ribonuclease such asbarnase is selectively expressed in the tapetum cells in the stamens.Fertility can then be restored by expression in the tapetum cells of aribonuclease inhibitor such as barstar.

Plants or plant varieties (obtained by plant biotechnology methods suchas genetic engineering) which may be treated according to the inventionare herbicide-tolerant plants, i.e. plants made tolerant to one or moregiven herbicides. Such plants can be obtained either by genetictransformation, or by selection of plants containing a mutationimparting such herbicide tolerance.

Herbicide-tolerant plants are for example glyphosate-tolerant plants,i.e. plants made tolerant to the herbicide glyphosate or salts thereof.For example, glyphosate-tolerant plants can be obtained by transformingthe plant with a gene encoding the enzyme5-enolpyruvylshikimate-3-phosphate synthase (EPSPS). Examples of suchEPSPS genes are the AroA gene (mutant CT7) of the bacterium Salmonellatyphimurium, the CP4 gene of the bacterium Agrobacterium sp., the genesencoding a petunia EPSPS, a tomato EPSPS, or an Eleusine EPSPS. It canalso be a mutated EPSPS. Glyphosate-tolerant plants can also be obtainedby expressing a gene that encodes a glyphosate oxidoreductase enzyme.Glyphosate-tolerant plants can also be obtained by expressing a genethat encodes a glyphosate acetyl transferase enzyme. Glyphosate-tolerantplants can also be obtained by selecting plants containingnaturally-occurring mutations of the above-mentioned genes.

Other herbicide-resistant plants are for example plants which have beenmade tolerant to herbicides inhibiting the enzyme glutamine synthase,such as bialaphos, phosphinothricin or glufosinate. Such plants can beobtained by expressing an enzyme detoxifying the herbicide or a mutantglutamine synthase enzyme that is resistant to inhibition. One suchefficient detoxifying enzyme is, for example, an enzyme encoding aphosphinothricin acetyltransferase (such as the bar or pat protein fromStreptomyces species). Plants expressing an exogenous phosphinothricinacetyltransferase have been described.

Further herbicide-tolerant plants are also plants that are made tolerantto the herbicides inhibiting the enzyme hydroxyphenylpyruvatedioxygenase(HPPD). Hydroxyphenylpyruvatedioxygenases are enzymes that catalyse thereaction in which para-hydroxyphenylpyruvate (HPP) is transformed intohomogentisate. Plants tolerant to HPPD-inhibitors can be transformedwith a gene encoding a naturally-occurring resistant HPPD enzyme, or agene encoding a mutated HPPD enzyme. Tolerance to HPPD-inhibitors canalso be obtained by transforming plants with genes encoding certainenzymes enabling the formation of homogentisate despite the inhibitionof the native HPPD enzyme by the HPPD-inhibitor. Tolerance of plants toHPPD inhibitors can also be improved by transforming plants with a geneencoding an enzyme prephenate dehydrogenase in addition to a geneencoding an HPPD-tolerant enzyme.

Further herbicide-resistant plants are plants that have been madetolerant to acetolactate synthase (ALS) inhibitors. Known ALS inhibitorsinclude, for example, sulphonylurea, imidazolinone, triazolopyrimidines,pyrimidinyloxy(thio)benzoates, and/or sulphonylaminocarbonyltriazolinoneherbicides. Different mutations in the ALS enzyme (also known asacetohydroxyacid synthase, AHAS) are known to confer tolerance todifferent herbicides and groups of herbicides. The production ofsulphonylurea-tolerant plants and imidazolinone-tolerant plants has beendescribed in the international publication WO 1996/033270. Furthersulphonylurea- and imidazolinone-tolerant plants have also beendescribed, for example in WO 2007/024782.

Other plants tolerant to imidazolinone and/or sulphonylurea can beobtained by induced mutagenesis, by selection in cell cultures in thepresence of the herbicide or by mutation breeding. Plants or plantvarieties (obtained by plant biotechnology methods such as geneticengineering) which may also be treated according to the invention areinsect-resistant transgenic plants, i.e. plants made resistant to attackby certain target insects. Such plants can be obtained by genetictransformation, or by selection of plants containing a mutationimparting such insect resistance.

In the present context, the term “insect-resistant transgenic plant”includes any plant containing at least one transgene comprising a codingsequence encoding:

-   1) an insecticidal crystal protein from Bacillus thuringiensis or an    insecticidal portion thereof, such as the insecticidal crystal    proteins listed online at:    http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/, or    insecticidal portions thereof, for example proteins of the Cry    protein classes Cry1Ab, Cry1Ac, Cry1F, Cry2Ab, Cry3Ae or Cry3Bb or    insecticidal portions thereof; or-   2) a crystal protein from Bacillus thuringiensis or a portion    thereof which is insecticidal in the presence of a second other    crystal protein from Bacillus thuringiensis or a portion thereof,    such as the binary toxin made up of the Cy34 and Cy35 crystal    proteins; or-   3) a hybrid insecticidal protein comprising parts of two different    insecticidal crystal proteins from Bacillus thuringiensis, such as a    hybrid of the proteins of 1) above or a hybrid of the proteins of 2)    above, for example the Cry1A.105 protein produced by maize event    MON98034 (WO 2007/027777); or-   4) a protein of any one of 1) to 3) above wherein some, particularly    1 to 10, amino acids have been replaced by another amino acid to    obtain a higher insecticidal activity to a target insect species,    and/or to expand the range of target insect species affected, and/or    because of changes induced in the encoding DNA during cloning or    transformation, such as the Cry3Bb1 protein in maize events MON863    or MON88017, or the Cry3A protein in maize event MIR604;-   5) an insecticidal secreted protein from Bacillus thuringiensis or    Bacillus cereus, or an insecticidal portion thereof, such as the    vegetative insecticidal proteins (VIP) listed at:    http://www.lifesci.sussex.ac.uk/home/Neil_Crickmore/Bt/vip.html, for    example proteins from the VIP3Aa protein class; or-   6) a secreted protein from Bacillus thuringiensis or Bacillus cereus    which is insecticidal in the presence of a second secreted protein    from Bacillus thuringiensis or B. cereus, such as the binary toxin    made up of the VIP1A and VIP2A proteins.-   7) a hybrid insecticidal protein comprising parts from different    secreted proteins from Bacillus thuringiensis or Bacillus cereus,    such as a hybrid of the proteins in 1) above or a hybrid of the    proteins in 2) above; or-   8) a protein of any one of 1) to 3) above wherein some, particularly    1 to 10, amino acids have been replaced by another amino acid to    obtain a higher insecticidal activity to a target insect species,    and/or to expand the range of target insect species affected, and/or    because of changes induced in the encoding DNA during cloning or    transformation (while still encoding an insecticidal protein), such    as the VIP3Aa protein in cotton event COT102.

Of course, insect-resistant transgenic plants, as used herein, alsoinclude any plant comprising a combination of genes encoding theproteins of any one of the above classes 1 to 8. In one embodiment, aninsect-resistant plant contains more than one transgene encoding aprotein of any one of the above classes 1 to 8, to expand the range oftarget insect species affected or to delay insect resistance developmentto the plants, by using different proteins insecticidal to the sametarget insect species but having a different mode of action, such asbinding to different receptor binding sites in the insect.

Plants or plant varieties (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are tolerant to abiotic stress factors. Such plants can beobtained by genetic transformation, or by selection of plants containinga mutation imparting such stress resistance. Particularly usefulstress-tolerant plants include the following:

-   a. plants which contain a transgene capable of reducing the    expression and/or the activity of the poly(ADP-ribose)polymerase    (PARP) gene in the plant cells or plants.-   b. plants which contain a stress tolerance-enhancing transgene    capable of reducing the expression and/or the activity of the PARG    encoding genes of the plants or plants cells;-   c. plants which contain a stress tolerance-enhancing transgene    coding for a plant-functional enzyme of the nicotinamide adenine    dinucleotide salvage biosynthesis pathway, including nicotinamidase,    nicotinate phosphoribosyltransferase, nicotinic acid mononucleotide    adenyl transferase, nicotinamide adenine dinucleotide synthetase or    nicotinamide phosphoribosyltransferase.

Plants or plant varieties (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention show altered quantity, quality and/or storage-stability of theharvested product and/or altered properties of specific ingredients ofthe harvested product such as, for example:

-   1) Transgenic plants which synthesize a modified starch which is    altered with respect to its chemophysical traits, in particular the    amylose content or the amylose/amylopectin ratio, the degree of    branching, the average chain length, the distribution of the side    chains, the viscosity behavior, the gel resistance, the grain size    and/or grain morphology of the starch in comparison to the    synthesized starch in wild-type plant cells or plants, such that    this modified starch is better suited for certain applications.-   2) Transgenic plants which synthesize non-starch carbohydrate    polymers or which synthesize non-starch carbohydrate polymers with    altered properties in comparison to wild type plants without genetic    modification. Examples are plants which produce polyfructose,    especially of the inulin and levan type, plants which produce    alpha-1,4-glucans, plants which produce alpha-1,6 branched    alpha-1,4-glucans, and plants producing alternan-   3) Transgenic plants which produce hyaluronan.

Plants or plant varieties (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are plants, such as cotton plants, with altered fibercharacteristics. Such plants can be obtained by genetic transformation,or by selection of plants containing a mutation imparting such alteredfiber characteristics and include:

-   a) plants, such as cotton plants, which contain an altered form of    cellulose synthase genes,-   b) plants, such as cotton plants, which contain an altered form of    rsw2 or rsw3 homologous nucleic acids;-   c) plants, such as cotton plants, with an increased expression of    sucrose phosphate synthase;-   d) plants, such as cotton plants, with an increased expression of    sucrose synthase;-   e) plants, such as cotton plants, wherein the timing of the    plasmodesmatal gating at the basis of the fiber cell is altered, for    example through downregulation of fiber-selective β-1,3-glucanase;-   f) plants, such as cotton plants, which have fibers with altered    reactivity, for example through the expression of the    N-acetylglucosaminetransferase gene including nodC and chitin    synthase genes.

Plants or plant cultivars (that can be obtained by plant biotechnologymethods such as genetic engineering) which may also be treated accordingto the invention are plants, such as oilseed rape or related Brassicaplants, with altered oil profile characteristics. Such plants can beobtained by genetic transformation or by selection of plants containinga mutation imparting such altered oil characteristics and include:

-   a) plants, such as oilseed rape plants, which produce oil having a    high oleic acid content;-   b) plants, such as oilseed rape plants, which produce oil having a    low linolenic acid content.-   c) plants, such as oilseed rape plants, which produce oil having a    low level of saturated fatty acids.

Particularly useful transgenic plants which may be treated according tothe invention are plants which comprise one or more genes which encodeone or more toxins are the transgenic plants available under thefollowing trade names' YIELD GARD® (for example maize, cotton, soyabeans), KnockOut® (for example maize), BiteGard® (for example maize),BT-Xtra® (for example maize), StarLink® (for example maize), Bollgard®(cotton), Nucotn® (cotton), Nucotn 33B® (cotton), NatureGard® (forexample maize), Protecta® and NewLeaf® (potato). Examples ofherbicide-tolerant plants which may be mentioned are maize varieties,cotton varieties and soya bean varieties which are available under thefollowing trade names: Roundup Ready® (tolerance to glyphosate, forexample maize, cotton, soya beans), Liberty Link® (tolerance tophosphinothricin, for example oilseed rape), IMI® (tolerance toimidazolinone) and SCS® (tolerance to sulphonylurea, for example maize).Herbicide-resistant plants (plants bred in a conventional manner forherbicide tolerance) which may be mentioned include the varieties soldunder the name Clearfield® (for example maize).

Particularly useful transgenic plants which may be treated according tothe invention are plants containing transformation events, or acombination of transformation events, that are listed for example in thedatabases for various national or regional regulatory agencies (see forexample http://gmoinfo.jrc it/gmp_browse.aspx andhttp://www.agbios.com/dbase.php).

The plants listed can be treated according to the invention in aparticularly advantageous manner with the compounds of the generalformula (I) and/or the active compound mixtures according to theinvention. The preferred ranges stated above for the active compounds ormixtures also apply to the treatment of these plants. Particularemphasis is given to the treatment of plants with the compounds ormixtures specifically mentioned in the present text.

The active compounds or compositions according to the invention can thusbe employed for protecting plants for a certain period of time aftertreatment against attack by the pathogens mentioned. The period forwhich protection is provided extends generally for 1 to 28 days,preferably 1 to 14 days, particularly preferably for 1 to 10 days, veryparticularly preferably for 1 to 7 days after the treatment of theplants with the active compounds, or up to 200 days after a seedtreatment.

The preparation and the use of the active compounds of the formula (I)according to the invention is illustrated by the examples below.However, the invention is not limited to these examples.

General note: Unless indicated otherwise, all chromatographicpurification and separation steps are carried out on silica gel andusing a solvent gradient of from 0:100 ethyl acetate/cyclohexane to100:0 ethyl acetate/cyclohexane.

General note: Unless indicated otherwise, all chromatographicpurification and separation steps are carried out on silica gel andusing a solvent gradient of from 0:100 ethyl acetate/hexane to 100:0ethyl acetate/hexane.

PREPARATION OF STARTING MATERIALS OF THE FORMULA (XVIII)3-tert-Butyl-5-(pentafluoroethyl)-1H-pyrazole (XVIII-1)

At room temperature, hydrazine hydrate (2.06 g) is added to a solutionof 1,1,1,2,2-pentafluoro-6,6-dimethylheptane-3,5-dione (10.1 g) inethanol (100 ml). The reaction mixture is stirred at room temperatureovernight. After removal of the solvents under reduced pressure,3-tert-butyl-5-(pentafluoroethyl)-1H-pyrazole (7.9 g, 79%) is obtained.

logP (pH 2.7): 3.23

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.30 (s, 9H), 6.40 (s, 1H) 13.3 (s,1H)

MS (ESI): 243 ([M+H]⁺)

5-tert-Butyl-3-(trifluoromethyl)-1H-pyrazole (XVIII-2)

1,1,1-Trifluoro-5,5-dimethylhexane-2,4-dione (14.1 g) is reactedanalogously to Example XVIII-1 with hydrazine hydrate (3.61 g). Thisgives 5-tert-butyl-3-(trifluoromethyl)-1H-pyrazole (10.7 g, 77%)

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.30 (s, 9H), 6.39 (s, 1H), 13.1 (s,1H)

MS (ESI): 192 ([M]^(.+))

3-Isopropyl-5-(trifluoromethyl)-1H-pyrazole (XVIII-3)

1,1,1-Trifluoro-5-methylhexane-2,4-dione (24.9 g) is reacted analogouslyto Example XVIII-1 with hydrazine hydrate (6.84 g). This gives3-isopropyl-5-(trifluoromethyl)-1H-pyrazole (19 g, 78%)

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.23 (d, 6H), 3.02 (septet, 1H),6.39 (s, 1H), 13.1 (s, 1H)

MS (ESI): 178 ([M]^(.+))

PREPARATION OF STARTING MATERIALS OF THE FORMULA (XVI) Ethyl[3-tert-butyl-5-(trifluoromethyl)-1H-pyrazol-1-yl]acetate (XVI-1) andethyl [5-tert-butyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetate (XVI-2)

Potassium carbonate (15.4 g) is added to a solution of5-tert-butyl-3-(trifluoromethyl)-1H-pyrazole (XVIII-2, 10.7 g) inacetonitrile (150 ml). Ethyl bromoacetate (13.9 g) is then addeddropwise at room temperature. The reaction mixture is stirred at roomtemperature overnight and then filtered and concentrated under reducedpressure. The residue is purified chromatographically. This gives ethyl[3-tert-butyl-5-(trifluoromethyl)-1H-pyrazol-1-yl]acetate (7.84 g, 50%)and ethyl [5-tert-butyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetate(4.53 g, 29%).

Ethyl [3-tert-butyl-5-(trifluoromethyl)-1H-pyrazol-1-yl]acetate (XVI-1)

logP (pH 2.7): 3.89

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.18 (t, 3H), 1.26 (s, 9H), 4.15 (q,2H), 5.06 (s, 2H), 6.79 (s, 1H)

MS (ESI): 279 ([M+H]⁺)

Ethyl [5-tert-butyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetate (XVI-2)

logP (pH 2.7): 3.48

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.20 (t, 3H), 1.31 (s, 9H), 4.17 (q,2H), 5.18 (s, 2H), 6.47 (s, 1H)

MS (ESI): 279 ([M+H]⁺)

Ethyl [3-tert-butyl-5-(pentafluoroethyl)-1H-pyrazol-1-yl]acetate (XVI-3)and ethyl [5-tert-butyl-3-(pentafluoroethyl)-1H-pyrazol-1-yl]acetate(XVI-4)

3-tert-Butyl-5-(pentafluoroethyl)-1H-pyrazole (XVIII-1, 7.90 g) isreacted analogously to Examples XVI-1 and XVI-2 with ethyl bromoacetate(8.17 g). This gives, after chromatographic purification, ethyl[3-tert-butyl-5-(pentafluoroethyl)-1H-pyrazol-1-yl]acetate (2.50 g, 23%)and ethyl [5-tert-butyl-3-(pentafluoroethyl)-1H-pyrazol-1-yl]acetate(4.80 g, 45%).

Ethyl [3-tert-butyl-5-(pentafluoroethyl)-1H-pyrazol-1-yl]acetate (XVI-3)

logP (pH 2.7): 4.45

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.18 (t, 3H), 1.26 (s, 9H), 4.15 (q,2H), 5.07 (s, 2H), 6.75 (s, 1H)

MS (ESI): 329 ([M+H]⁺)

Ethyl [5-tert-butyl-3-(pentafluoroethyl)-1H-pyrazol-1-yl]acetate (XVI-4)

logP (pH 2.7): 4.05

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.18 (t, 3H), 1.32 (s, 9H), 4.16 (q,2H), 5.20 (s, 2H), 6.47 (s, 1H)

MS (ESI): 329 ([M+H]⁺)

Ethyl [3-isopropyl-5-(trifluoromethyl)-1H-pyrazol-1-yl]acetate (XVI-5)

3-Isopropyl-5-(trifluoromethyl)-1H-pyrazole (XVIII-3, 19.3 g) is reactedanalogously to Examples XVI-1 and XVI-2 with ethyl bromoacetate (27.1g). This gives ethyl[3-isopropyl-5-(trifluoromethyl)-1H-pyrazol-1-yl]acetate (26.2 g, 92%)

logP (pH 2.7): 3.22

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.18-1.22 (m, 3H), 1.20 (d, 6H), 3.0(septet, 1H), 4.17 (q, 2H), 5.11 (s, 2H), 6.54 (s, 1H)

MS (ESI): 265 ([M+H]⁺)

Ethyl [4-chloro-5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetate(XVI-6)

4-Chloro-5-methyl-3-(trifluoromethyl)-1H-pyrazole (14.9 g) is reactedanalogously to Examples XVI-1 and XVI-2 with ethyl bromoacetate (20.3g). This gives ethyl[4-chloro-5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetate (19.5 g,89%)

logP (pH 2.7): 3.11

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.22 (t, 3H), 2.25 (s, 3H), 4.18 (q,2H), 5.24 (s, 2H)

MS (ESI): 271 ([M+H]⁺)

PREPARATION OF STARTING MATERIALS OF THE FORMULA (V)[3-tert-Butyl-5-(trifluoromethyl)-1H-pyrazol-1-yl]acetic acid (V-1)

At room temperature, a solution of lithium hydroxide monohydrate (2.35g) in water (20 ml) is added dropwise to a solution of ethyl[3-tert-butyl-5-(trifluoromethyl)-1H-pyrazol-1-yl]acetate (XVI-1, 7.80g) in tetrahydrofuran (80 ml). The reaction mixture is stirred for 2hours. After removal of the solvent under reduced pressure, the residueis, at 0° C., slowly adjusted to pH 2-3 using dilute hydrochloric acid(1M). This gives, after filtration and drying,[3-tert-butyl-5-(trifluoromethyl)-1H-pyrazol-1-yl]acetic acid as a whitesolid (7.1 g, 100%).

logP (pH 2.7): 2.45

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.26 (s, 9H), 4.95 (s, 2H), 6.76 (s,1H)

MS (ESI): 251 ([M+H]

[5-tert-Butyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetic acid (V-2)

Ethyl [5-tert-butyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetate (XVI-2,4.50 g) is reacted analogously to Example V-1. This gives, afterfiltration and drying,[5-tert-butyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetic acid (3.9 g,95%).

logP (pH 2.7): 2.45

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.26 (s, 9H), 4.95 (s, 2H), 6.76 (s,1H)

MS (ESI): 251 ([M+H]⁺)

[3-tert-Butyl-5-(pentafluoroethyl)-1H-pyrazol-1-yl]acetic acid (V-3)

Ethyl [3-tert-butyl-5-(pentafluoroethyl)-1H-pyrazol-1-yl]acetate (XVI-3,2.50 g) is reacted analogously to Example V-1. This gives, afterfiltration and drying,[3-tert-butyl-5-(pentafluoroethyl)-1H-pyrazol-1-yl]acetic acid (1.8 g,79%).

logP (pH 2.7): 2.92

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.27 (s, 9H), 4.96 (s, 2H), 6.72 (s,1H)

MS (ESI): 301 ([M+H]⁺)

[5-tert-Butyl-3-(pentafluoroethyl)-1H-pyrazol-1-yl]acetic acid (V-4)

Ethyl [5-tert-butyl-3-(pentafluoroethyl)-1H-pyrazol-1-yl]acetate (XVI-4,4.80 g) is reacted analogously to Example V-1. This gives, afterfiltration and drying,[5-tert-butyl-3-(pentafluoroethyl)-1H-pyrazol-1-yl]acetic acid (3.5 g,80%).

logP (pH 2.7): 2.75

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.33 (s, 9H), 5.09 (s, 2H), 6.45 (s,1H)

MS (ESI): 301 ([M+H]⁺)

[3-Isopropyl-5-(trifluoromethyl)-1H-pyrazol-1-yl]acetic acid (V-5)

Ethyl [3-isopropyl-5-(trifluoromethyl)-1H-pyrazol-1-yl]acetate (XVI-5,26.2 g) is reacted analogously to Example V-1. This gives, afterfiltration and drying,[3-isopropyl-5-(trifluoromethyl)-1H-pyrazol-1-yl]acetic acid (22 g,94%).

logP (pH 2.7): 2.05

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.21 (d, 6H), 2.99 (septet, 1H),4.99 (s, 2H), 6.51 (s, 1H)

MS (ESI): 237 ([M+H]⁺)

[4-Chloro-5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetic acid (V-6)

Ethyl [4-chloro-5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetate(XVI-6, 18.0 g) is reacted analogously to Example V-1. This gives, afterfiltration and drying,[4-chloro-5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetic acid (15.5g, 96%).

logP (pH 7.8): 0.68

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 2.24 (s, 3H), 3.13 (bs, 1H), 5.04(s, 2H)

PREPARATION OF STARTING MATERIALS OF THE FORMULA (VI)4-[4-(Ethoxycarbonyl)-1,3-thiazol-2-yl]piperidinium chloride (VI-1)

Under argon and at 0° C., a 2-molar solution of hydrogen chloride indiethyl ether (370 ml) is added dropwise to a solution of tert-butyl4-[4-(ethoxycarbonyl)-1,3-thiazol-2-yl]piperidine-1-carboxylate (25.0 g)in diethyl ether (200 ml). The reaction mixture is stirred at 0° C. andthen slowly warmed to room temperature. After stirring overnight, thesolvent and excess hydrogen chloride are removed. This gives4-[4-(ethoxycarbonyl)-1,3-thiazol-2-yl]piperidinium chloride (20.0 g,98%)

logP (pH 2.7): 0.42

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.31 (t, 3H), 1.97-2.04 (m, 2H),2.18-2.23 (m, 2H), 2.98-3.08 (m, 2H), 3.31-3.39 (m, 2H), 3.42 (m, 1H),4.30 (q, 2H), 8.39 (s, 1H), 8.90 (bs, 1H), 9.13 (bs, 1H)

MS (ESI): 241 ([M-Cl]⁺)

3-[4-(Ethoxycarbonyl)-1,3-thiazol-2-yl]piperidinium chloride (VI-2)

tert-Butyl3-[4-(ethoxycarbonyl)-1,3-thiazol-2-yl]piperidine-1-carboxylate (13.8 g)is reacted analogously to Example VI-1. This gives3-[4-(ethoxycarbonyl)-1,3-thiazol-2-yl]piperidinium chloride (10.4 g,93%)

logP (pH 2.7): 0.54

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.31 (t, 3H), 1.75-1.82 (m, 1H),1.87-1.92 (m, 2H), 2.17-2.20 (m, 1H), 2.90-2.94 (m, 1H), 3.10-3.25 (m,1H), 3.25-3.28 (m, 1H), 3.57 (m, 1H), 3.62 (m, 1H), 4.30 (q, 2H), 8.43(s, 1H), 9.29-9.34 (m, 2H)

MS (ESI): 241 ([M-Cl]⁺)

PREPARATION OF STARTING MATERIALS OF THE FORMULA (IV) Ethyl2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(IV-1)

Oxalyl chloride (6.91 g) and a drop of N,N-dimethylformamide are addedto a solution of [3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetic acid(8.00 g) in dichloromethane (200 ml). The reaction mixture is stirred atroom temperature overnight, and excess oxalyl chloride is then removedunder reduced pressure. The residue is redissolved in dichloromethane(20 ml) and added to a solution of4-[4-(ethoxycarbonyl)-1,3-thiazol-2-yl]piperidinium chloride (VI-1, 7.53g) and Hünig base (10.6 g) in dichloromethane (80 ml). The reactionmixture is stirred at room temperature for 24 hours, added to a mixtureof ice and water, neutralized with saturated bicarbonate solution andextracted with ethyl acetate. The combined organic phases are dried oversodium sulphate and concentrated under reduced pressure. The residue ispurified chromatographically. This gives ethyl2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(10 g, 63%).

logP (pH 2.7): 2.52

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.31 (t, 3H), 1.55-1.85 (m, 2H),2.10 (m, 2H), 3.20-3.60 (m, 4H), 3.99 (bs, 1H), 4.30 (q, 2H), 5.35 (s,2H), 6.83-7.30 (m, 3H), 8.37 (s, 1H)

MS (ESI): 449 ([M+H]⁺)

Ethyl2-(1-{[3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(IV-2)

4-[4-(Ethoxycarbonyl)-1,3-thiazol-2-yl]piperidinium chloride (VI-1, 5.50g) is reacted analogously to Example IV-1 with[3-(trifluoromethyl)-1H-pyrazol-1-yl]acetic acid (3.86 g). This gives,after chromatographic purification, ethyl2-(1-{[3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(5.1 g, 62%).

logP (pH 2.7): 2.41

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.31 (t, 3H), 1.63 (bs, 1H), 1.75(bs, 1H), 2.05-2.15 (m, 2H), 2.88 (bs, 1H), 3.26 (bs, 1H), 3.36 (m, 1H),3.98 (bs, 1H), 4.30 (q, 2H), 4.35 (bs, 1H), 5.28 (s, 2H), 6.67 (d, 1H),7.85 (dd, 1H), 8.36 (s, 1H)

MS (ESI): 417 ([M+H]⁺)

Ethyl2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-3-yl)-1,3-thiazole-4-carboxylate(IV-3)

3-[4-(Ethoxycarbonyl)-1,3-thiazol-2-yl]piperidinium chloride (VI-2, 5.32g) is reacted analogously to Example IV-1 with[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetic acid (4.00 g). Thisgives, after chromatographic purification, ethyl2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-3-yl)-1,3-thiazole-4-carboxylate(5.7 g, 69%).

logP (pH 2.7): 2.78

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.29 (t, 3H), 1.50-1.74 (m, 2H),1.79-1.89 (m, 2H), 2.20 (s, 3H), 3.18 (m, 1H), 3.39 (m, 0.5H), 3.69 (m,0.5H), 3.86-3.89 (m, 1H), 4.00 (m, 0.5H), 4.30 (q, 2H), 4.45 (m, 0.5H),4.90 (m, 1H), 5.25-5.30 (m, 2H), 6.44 (s, 1H), 8.40 (s, 1H)

MS (ESI): 431 ([M+H]⁺)

Ethyl2-{1-[2-(3,5-dimethyl-1H-pyrazol-1-yl)-2-methylpropanoyl]piperidin-4-yl}-1,3-thiazole-4-carboxylate(IV-4)

4-[4-(Ethoxycarbonyl)-1,3-thiazol-2-yl]piperidinium chloride (VI-1, 8.23g) is reacted analogously to Example IV-1 with2-(3,5-dimethyl-1H-pyrazol-1-yl)-2-methylpropanoic acid (5.42 g). Thisgives, after chromatographic purification, ethyl2-{1-[2-(3,5-dimethyl-1H-pyrazol-1-yl)-2-methylpropanoyl]piperidin-4-yl}-1,3-thiazole-4-carboxylate(9.64 g, 80%)

logP (pH 7.8): 2.34

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.29 (t, 3H), 1.41 (m, 2H), 1.66 (s,6H), 1.90 (m, 2H), 2.11 (s, 3H), 2.12 (s, 3H), 2.81 (m, 2H), 3.22 (m,1H), 3.59 (m, 1H), 4.10 (m, 1H), 4.28 (q, 2H), 5.89 (s, 1H), 8.32 (s,1H)

MS (ESI): 405 ([M+H]⁺)

Ethyl2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(IV-5)

4-[4-(Ethoxycarbonyl)-1,3-thiazol-2-yl]piperidinium chloride (VI-1, 4.65g) is reacted analogously to Example IV-1 with[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetic acid (3.50 g). Thisgives, after chromatographic purification, ethyl2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(5.00 g, 69%).

logP (pH 2.7): 2.62

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.31 (t, 3H), 1.62 (bs, 1H), 1.80(bs, 1H), 2.06-2.16 (m, 2H), 2.22 (s, 3H), 2.88 (bs, 1H), 3.28 (bs, 1H),3.37 (m, 1H), 3.99 (bs, 1H), 4.30 (q, 2H), 4.33 (bs, 1H), 5.22 (bs, 2H),6.45 (s, 1H), 8.37 (s, 1H)

MS (ESI): 431 ([M+H]⁺)

Ethyl2-(1-{[4-chloro-5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(IV-6)

4-[4-(Ethoxycarbonyl)-1,3-thiazol-2-yl]piperidinium chloride (VI-1, 5.50g) is reacted analogously to Example IV-1 with[4-chloro-5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetic acid (4.82g). This gives, after chromatographic purification, ethyl2-(1-{[4-chloro-5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(6.00 g, 65%).

logP (pH 2.7): 3.17

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.31 (t, 3H), 1.61 (bs, 1H), 1.81(bs, 1H), 2.05-2.15 (m, 2H), 2.20 (s, 3H), 2.88 (bs, 1H), 3.27 (bs, 1H),3.37 (m, 1H), 3.95 (bs, 1H), 4.30 (q, 2H), 4.32 (bs, 1H), 5.27-5.35 (3,2H), 8.37 (s, 1H)

MS (ESI): 465 ([M+H]⁺)

PREPARATION OF STARTING MATERIALS OF THE FORMULA (III)2-(1-{[3,5-Bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylicacid (III-1)

Ethyl2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(IV-1, 13.3 g) is dissolved in tetrahydrofuran (80 ml). LiOH monohydrate(1.86 g) dissolved in water (20 ml) is then added. After 3 hours, wateris added, the pH is adjusted to 2-3 with dilute hydrochloric acid (1M),the mixture is then extracted with ethyl acetate and the combinedorganic phases are dried with sodium sulfate. The solid is filtered offand the solvent is removed by distillation. This gives2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylicacid (11.7 g, 94%).

logP (pH 2.7): 1.71

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.55-1.85 (m, 2H), 2.09-2.13 (m,2H), 2.80-3.30 (m, 3H), 3.36 (m, 1H), 3.99 (bs, 1H), 4.30 (bs, 1H), 5.34(s, 2H), 6.85 (s, 1H), 6.98 (t, 1H), 7.14 (t, 1H), 8.29 (s, 1H)

MS (ESI): 421 ([M+H]⁺)

2-(1-{[3-(Trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylicacid (III-2)

Ethyl2-(1-{[3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(IV-2, 5.20 g) is reacted analogously to Example III-1. This gives,after drying,2-(1-{[3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylicacid (4.6 g, 95%).

logP (pH 2.7): 1.65

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.64 (bs, 1H), 1.76 (bs, 1H),2.05-2.15 (m, 2H), 2.88 (bs, 1H), 3.23 (bs, 1H), 3.36 (m, 1H), 3.98 (bs,1H), 4.34 (bs, 1H), 5.28 (s, 2H), 6.67 (d, 1H), 7.85 (dd, 1H), 8.29 (s,1H)

MS (ESI): 389 ([M+H]⁺)

2-(1-{[5-Methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-3-yl)-1,3-thiazole-4-carboxylicacid (III-3)

Ethyl2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-3-yl)-1,3-thiazole-4-carboxylate(IV-3, 5.70 g) is reacted analogously to Example III-1. This gives,after drying,2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-3-yl)-1,3-thiazole-4-carboxylicacid (5.4 g, 100%).

logP (pH 2.7): 1.90

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.48-1.88 (m, 4H), 2.20 (s, 3H),3.38 (m, 0.5H), 3.60 (m, 0.5H), 3.87 (m, 2H), 4.01 (m, 0.5H), 4.45 (m,0.5H), 5.24-5.28 (m, 3H), 6.44 (s, 1H), 8.32 (s, 1H)

MS (ESI): 403 ([M+H]⁺)

2-(1-{[5-Methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylicacid (III-4)

Ethyl2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-5-yl)-1,3-thiazole-4-carboxylate(IV-3, 5.10 g) is reacted analogously to Example III-1. This gives,after drying,2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylicacid (4.63 g, 97%).

logP (pH 2.7): 1.82

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.62 (bs, 1H), 1.79 (bs, 1H),2.06-2.16 (m, 2H), 2.22 (s, 3H), 2.88 (bs, 1H), 3.28 (bs, 1H), 3.37 (m,1H), 3.99 (bs, 1H), 4.33 (bs, 1H), 5.21 (bs, 2H), 6.45 (d, 1H), 8.30 (s,1H)

MS (ESI): 403 ([M+H]⁺)

2-(1-{[4-Chloro-5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylicacid (III-5)

Ethyl2-(1-{[4-chloro-5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-5-yl)-1,3-thiazole-4-carboxylate(IV-6, 6.00 g) is reacted analogously to Example III-1. This gives,after drying,2-(1-{[4-chloro-5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylicacid (3.10 g, 55%).

logP (pH 2.7): 2.26

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm) 1.61 (bs, 1H), 1.81 (bs, 1H),2.05-2.17 (m, 2H), 2.20 (s, 3H), 2.89 (bs, 1H), 3.27 (bs, 1H), 3.37 (m,1H), 3.95 (bs, 1H), 4.32 (bs, 1H), 5.27-5.34 (m, 2H), 8.29 (s, 1H)

MS (ESI): 437 ([M+H]⁺)

PREPARATION OF THE COMPOUNDS OF THE FORMULA (I) Cyclohexyl2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(I-811)

At room temperature, cyclohexanol (2.17 g), dimethylaminopyridine (0.20g) and 1-ethyl-3-(3′-dimethylaminopropyl)carbodiimide (3.35 g) are addedto a solution of2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylicacid (III-1, 7.00 g) in dichloromethane (80 ml). The mixture is stirredovernight, and water is then added. The aqueous phase is separated offand extracted with ethyl acetate. The combined organic phases are driedwith sodium sulfate. The solid is filtered off and the solvent isremoved by distillation. The residue is purified chromatographically.This gives cyclohexyl2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(2.83 g, 34%).

logP (pH 2.7): 3.64

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.29-1.90 (m, 12H), 2.09-2.12 (m,2H), 2.88 (bs, 1H), 3.25 (bs, 1H), 3.39 (m, 1H), 4.01 (bs, 1H), 4.30(bs, 1H), 4.88-4.93 (m, 1H), 5.35 (s, 2H), 6.85 (s, 1H), 6.96 (t, 1H),7.14 (t, 1H), 8.34 (s, 1H)

MS (ESI): 503 ([M+H]⁺)

1-Naphthyl2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(I-813)

2-(1-{[3,5-Bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylicacid (III-1, 7.00 g) is reacted analogously to Example I-811 with1-naphthol (3.12 g). This gives, after chromatographic purification,1-naphthyl-2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(4.0 g, 44%).

logP (pH 2.7): 3.64

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.70 (bs, 1H), 1.87 (bs, 1H), 2.18(m, 2H), 2.91 (bs, 1H), 3.31 (bs, 1H), 3.48 (m, 1H), 4.03 (bs, 1H), 4.36(bs, 1H), 5.36 (s, 2H), 6.85 (s, 1H), 6.97 (t, 1H), 7.15 (t, 1H), 7.45(dd, 1H), 7.54-7.61 (m, 3H), 7.89 (m, 2H), 8.01 (m, 1H), 8.84 (s, 1H)

MS (ESI): 547 ([M+H]⁺)

1-Naphthyl2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(I-227)

Oxalyl chloride (189 mg) and a drop of N,N-dimethylformamide are addedto a solution of2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylicacid (III-4, 200 mg) in dichloromethane (2 ml). The reaction mixture isstirred at room temperature overnight, and excess oxalyl chloride isthen removed under reduced pressure. The residue is re-dissolved indichloromethane (2 ml) and added to a solution of 1-naphthol (79 mg) andpyridine (489 mg) in dichloromethane (4 ml). The mixture is stirred atroom temperature for one hour, and dilute hydrochloric acid (1M) is thenadded. The aqueous phase is separated off and extracted with ethylacetate, and the combined organic phases are then dried with sodiumsulfate. The solid is filtered off and the solvent is removed bydistillation. The residue is purified chromatographically. This gives1-naphthyl2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(100 mg, 38%).

logP (pH 2.7): 3.75

¹H NMR (CD₃CN, 400 MHz): δ_(ppm): 1.72-2.00 (m, 2H), 2.19-2.27 (m, 2H),2.24 (s, 3H), 2.92 (bs, 1H), 3.34 (bs, 1H), 3.42 (m, 1H), 3.98 (bs, 1H),4.49 (bs, 1H), 5.06 (bs, 2H), 6.37 (s, 1H), 7.40 (d, 1H), 7.52-7.60 (m,3H), 7.86 (d, 1H), 7.92-7.99 (m, 2H), 8.55 (s, 1H)

MS (ESI): 529 ([M+H]⁺)

1,2,3,4-Tetrahydronaphthalen-1-yl2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(I-224)

At room temperature, 1,2,3,4-tetrahydronaphthalen-1-ol (155 mg) andtriphenylphosphine (758 mg) are added to a solution of2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylicacid (III-4, 380 mg) in tetrahydrofuran (2.5 ml). The mixture is stirredat 0 C under argon for 5 minutes, and diethyldiazene 1,2-dicarboxylate(383 mg) is then added dropwise. The reaction mixture is slowly warmedto room temperature. After 2 hours, the solvent is removed under reducedpressure and the residue is purified chromatographically. This gives1,2,3,4-tetrahydronaphthalen-1-yl2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(196 mg, 39%).

logP (pH 2.7): 4.01

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.52-1.88 (m, 3H), 1.88-2.15 (m,4H), 2.22 (s, 3H), 2.70-2.99 (m, 4H), 3.25 (bs, 1H), 3.38 (m, 1H), 3.98(bs, 1H), 4.33 (bs, 1H), 5.21 (bs, 2H), 6.12 (t, 1H), 6.44 (s, 1H),7.15-7.19 (m, 2H), 7.21-7.30 (m, 2H), 8.35 (s, 1H)

MS (ESI): 403 ([M+H-1,2,3,4-tetrahydronaphthalen-1-ol]⁺)

Cyclohexyl2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(I-220)

A solution of2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylicacid (III-4, 6.00 g) is reacted analogously to Example I-811 withcyclohexanol (1.94 g). This gives, after chromatographic purification,cyclohexyl2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(5.00 g, 69%).

logP (pH 2.7): 3.74

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.25-1.48 (m, 3H), 1.50-2.00 (broadm, 2H), 1.50-1.51 (m, 3H), 1.70-1.80 (m, 2H), 1.85-1.92 (m, 2H),2.06-2.16 (m, 2H), 2.22 (s, 3H), 2.88 (bs, 1H), 3.28 (bs, 1H), 3.38 (m,1H), 3.98 (bs, 1H), 4.34 (bs, 1H), 4.91 (septet, 1H), 5.21 (bs, 2H),6.44 (s, 1H), 8.34 (s, 1H)

MS (ESI): 485 ([M+H]⁺)

2-Bromobenzyl2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(I-820)

A solution of2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylicacid (III-4, 100 mg) is reacted analogously to Example I-811 with(2-bromophenyl)methanol (49.0 mg). This gives, after chromatographicpurification, 2-bromobenzyl2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(123 mg, 89%).

logP (pH 2.7): 3.80

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.62 (bs, 1H), 1.80 (bs, 1H),2.07-2.19 (m, 2H), 2.22 (s, 3H), 2.88 (bs, 1H), 3.27 (bs, 1H), 3.38 (m,1H), 3.99 (bs, 1H), 4.43 (bs, 1H), 5.22 (bs, 2H), 5.38 (s, 2H), 6.44 (s,1H), 7.32 (td, 1H), 7.43 (td, 1H), 7.56 (dd, 1H), 7.67 (dd, 1H), 8.46(s, 1H)

MS (ESI): 571, 573 ([M+H]⁺)

3,3-Dimethylbutyl2-(1-{[3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(I-767)

A solution of2-(1-{[3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylicacid (III-2, 200 mg) is reacted analogously to Example I-811 with3,3-dimethylbutan-1-ol (68.0 mg). This gives, after chromatographicpurification, 3,3-dimethylbutyl2-(1-{[3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(98 mg, 40%).

logP (pH 2.7): 3.82

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 0.96 (s, 9H), 1.50-1.85 (broad m+t,4H), 2.06-2.13 (m, 2H), 2.88 (bs, 1H), 3.28 (bs, 1H), 3.38 (m, 1H), 3.98(bs, 1H), 4.31 (t, 2H), 4.34 (bs, 1H), 5.28 (bs, 2H), 6.66 (d, 1H), 7.85(s, 1H), 8.34 (s, 1H)

MS (ESI): 473 ([M+H]⁺)

S-(4-Fluorobenzyl)2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carbothioate(I-27)

A solution of2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylicacid (III-4, 200 mg) is reacted analogously to Example I-227 with(4-fluorophenyl)methanethiol (78.0 mg). This gives, afterchromatographic purification, S-(4-fluorobenzyl)2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carbothioate(110 mg, 42%).

logP (pH 2.7): 4.00

¹H NMR (CD₃CN, 400 MHz): δ_(ppm): 1.64-1.88 (broad m, 2H), 2.12-2.18 (m,2H), 2.23 (s, 3H), 2.92 (bs, 1H), 3.30 (bs, 1H), 3.33 (m, 1H), 3.97 (bs,1H), 4.24 (s, 2H), 4.41 (bs, 1H), 5.04 (bs, 2H), 6.36 (s, 1H), 7.00-7.07(m, 2H), 7.36-7.42 (m, 2H), 8.11 (s, 1H)

MS (ESI): 527 ([M+H]⁺)

S-Cyclohexyl2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carbothioate(I-76)

A solution of2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylicacid (III-4, 200 mg) is reacted analogously to Example I-227 withcyclohexanethiol (64.0 mg). This gives, after chromatographicpurification, S-cyclohexyl2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carbothioate(110 mg, 44%).

logP (pH 2.7): 4.51

¹H NMR (CD₃CN, 400 MHz): δ_(ppm): 1.30-1.40 (m, 2H), 1.42-1.90 (m, 10H),2.12-2.19 (m, 2H), 2.24 (s, 3H), 2.91 (bs, 1H), 3.30 (bs, 1H), 3.34 (m,1H), 3.65 (m, 1H), 3.95 (bs, 1H), 4.44 (bs, 1H), 5.04 (bs, 2H), 6.36 (s,1H), 8.05 (s, 1H)

MS (ESI): 501 ([M+H]⁺)

S-1-Naphthyl2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carbothioate(I-77)

A solution of2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylicacid (III-4, 200 mg) is reacted analogously to Example I-227 withnaphthalene-1-thiol (88.0 mg). This gives, after chromatographicpurification, S-1-naphthyl2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carbothioate(100 mg, 37%).

logP (pH 2.7): 4.22

¹H NMR (CD₃CN, 400 MHz): δ_(ppm): 1.74-1.90 (m, 2H), 2.20-2.26 (m, 2H),2.25 (s, 3H), 2.93 (bs, 1H), 3.34 (bs, 1H), 3.42 (m, 1H), 4.04 (bs, 1H),4.48 (bs, 1H), 5.07 (bs, 2H), 6.37 (s, 1H), 7.54-7.60 (m, 3H), 7.80 (dd,1H), 7.98 (dd, 1H), 8.05 (d, 1H), 8.13 (s, 1H), 8.20 (dd, 1H)

MS (ESI): 545 ([M+H]⁺)

PREPARATION OF STARTING MATERIALS OF THE FORMULA (VIII)2-[1-(tert-Butoxycarbonyl)piperidin-4-yl]-1,3-thiazole-4-carboxylic acid(VIII-1)

At room temperature, lithium hydroxide monohydrate (8.88 g) is added inone portion to a solution of tent-butyl4-[4-(ethoxycarbonyl)-1,3-thiazol-2-yl]piperidine-1-carboxylate (24.0 g)in tetrahydrofuran (240 ml) and water (60 ml). The mixture is stirredfor 4 hours and then stirred with dilute hydrochloric acid (1M) (100 ml)and ethyl acetate (100 ml). The aqueous phase is separated off andextracted with ethyl acetate, and the combined organic phases are thendried with sodium sulfate. The solid is filtered off and the solvent isremoved by distillation. This gives2-[1-(tert-Butoxycarbonyl)piperidin-4-yl]-1,3-thiazole-4-carboxylic acid(21 g, 94%)

logP (pH 2.7): 2.04

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.41 (s, 9H), 1.59 (qd, 2H), 2.02(dd, 2H), 2.91 (m, 2H), 3.23 (m, 1H), 3.97-4.02 (m, 2H), 8.27 (s, 1H)

MS (ESI): 256 ([M+H—C(CH₃)₃]⁺)

PREPARATION OF STARTING MATERIALS OF THE FORMULA (IX) tert-Butyl4-{4-[(cyclohexyloxy)carbonyl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(IX-1)

At room temperature, cyclohexanol (1.21 g), dimethylaminopyridine (113mg) and 1-ethyl-3-(3′-dimethylaminopropyl)carbodiimide (1.87 g) areadded to a solution of2-[1-(tert-butoxycarbonyl)piperidin-4-yl]-1,3-thiazole-4-carboxylic acid(VIII-1, 2.90 g) in dichloromethane (30 ml). The mixture is stirred atroom temperature overnight, and water is then added. The aqueous phaseis separated off and extracted with ethyl acetate, and the combinedorganic phases are then dried with sodium sulfate. The solid is filteredoff and the solvent is removed by distillation. The residue is purifiedchromatographically. This gives tert-butyl4-{4-[(cyclohexyloxy)carbonyl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(2.63 g, 72%)

logP (pH 2.7): 4.62

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.13-1.81 (m+s, 21H), 2.02 (m, 2H),2.90 (m, 2H), 3.40 (m, 1H), 3.98-4.01 (m, 2H), 4.90 (m, 1H), 8.32 (s,1H)

MS (ESI): 339 ([M+2H—C(CH₃)₃]⁺)

tert-Butyl4-{4-[(1-naphthyloxy)carbonyl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(IX-2)

A solution of2-[1-(tert-butoxycarbonyl)piperidin-4-yl]-1,3-thiazole-4-carboxylic acid(VIII-1, 12.0 g) is reacted analogously to Example IX-1 with 1-naphthol(7.20 g). This gives, after chromatographic purification, tert-butyl4-{4-[(1-naphthyloxy)carbonyl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(12.3 g, 73%)

logP (pH 2.7): 4.50

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.42 (s, 9H), 1.67 (qd, 2H), 2.10(dd, 2H), 2.95 (m, 2H), 3.35 (m, 1H), 4.00-4.08 (m, 2H), 7.45 (dd, 1H),7.55-7.62 (m, 3H), 7.89 (d, 2H), 8.01 (dd, 1H), 8.83 (s, 1H)

MS (ESI): 383 ([M+2H—C(CH₃)₃]⁺)

PREPARATION OF STARTING MATERIALS OF THE FORMULA (X)4-{4-[(Cyclohexyloxy)carbonyl]-1,3-thiazol-2-yl}piperidinium chloride(X-1)

Under argon and at 0° C., a 2-molar solution of hydrogen chloride indiethyl ether (50 ml) is added dropwise to a solution of tert-butyl4-{4-[(cyclohexyloxy)carbonyl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(IX-1, 2.63 g) in dioxane (20 ml). The reaction mixture is stirred at 0°C. and then slowly warmed to room temperature. After stirring overnight,the solvent and excess hydrogen chloride are removed. This gives4-{4-[(cyclohexyloxy)carbonyl]-1,3-thiazol-2-yl}piperidinium chloride(2.19 g, 99%)

logP (pH 2.7): 1.25

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.15-1.55 (m, 6H), 1.71-1.75 (m,2H), 1.85-1.90 (m, 2H), 1.98-2.04 (m, 2H), 2.20 (dd, 2H), 3.01-3.03 (m,2H), 3.14-3.34 (m, 2H), 3.40 (m, 1H), 4.90 (m, 1H), 8.36 (s, 1H), 9.05(bs, 1H), 9.25 (bs, 1H)

MS (ESI): 295 ([M-Cl]⁺)

4-{4-[(1-Naphthyloxy)carbonyl]-1,3-thiazol-2-yl}piperidinium chloride(X-2)

tert-Butyl4-{4-[(1-naphthyloxy)carbonyl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(IX-2, 3.20 g) is reacted analogously to Example X-1. This gives, afterdrying, 4-{4-[(1-naphthyloxy)carbonyl]-1,3-thiazol-2-yl}piperidiniumchloride (2.93 g, 100%)

logP (pH 2.7): 1.42

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 2.02-2.15 (m, 2H), 2.25-2.34 (m,2H), 3.00-3.12 (m, 2H), 3.34-3.40 (m, 2H), 3.51 (m, 1H), 7.46 (dd, 1H),7.53-7.62 (m, 3H), 7.89 (d, 2H), 8.00-5.05 (m, 1H), 8.87 (s, 1H), 9.05(bs, 1H), 9.25 (bs, 1H)

MS (ESI): 339 ([M−Cl]⁺)

PREPARATION OF THE COMPOUNDS OF THE FORMULA (I) Cyclohexyl2-(1-{[3,5-bis(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(I-772)

[3,5-Bis(trifluoromethyl)-1H-pyrazol-1-yl]acetic acid (288 mg) and Hünigbase (323 mg) are dissolved in dichloromethane (10 ml) and stirred atroom temperature for 30 min.4-{4-[(Cyclohexyloxy)carbonyl]-1,3-thiazol-2-yl}piperidinium chloride(X-1, 330 mg) is added, and the mixture is stirred for a further 5 minbefore bromo-tris-pyrrolidinophosphonium hexafluorophosphate (559 mg) isadded. The reaction mixture is stirred at room temperature overnight.After removal of the solvent under reduced pressure, the residue ispurified chromatographically. This gives cyclohexyl2-(1-{[3,5-bis(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(348 mg, 65%).

logP (pH 2.7): 4.39

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.20-1.60 (m, 8H), 1.71-1.75 (m,2H), 1.85-1.88 (m, 2H), 2.04 (m, 2H), 2.90 (bs, 1H), 3.30 (bs, 1H), 3.38(m, 1H), 3.95 (bs, 1H), 4.30 (bs, 1H), 4.91 (m, 1H), 5.48 (bs, 2H), 7.47(s, 1H), 8.34 (s, 1H)

MS (ESI): 539 ([M+H]⁺)

1-Naphthyl2-(1-{[3,5-bis(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(I-771)

4-{4-[(1-Naphthyloxy)carbonyl]-1,3-thiazol-2-yl}piperidinium chloride(X-2, 375 mg) is reacted analogously to Example I-772 with[3,5-bis(trifluoromethyl)-1H-pyrazol-1-yl]acetic acid (288 mg). Thisgives, after chromatographic purification, 1-naphthyl2-(1-{[3,5-bis(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate (356 mg,61%).

logP (pH 2.7): 4.35

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.65 (m, 1H), 1.90 (m, 1H), 2.19 (m,2H), 2.95 (m, 1H), 3.32 (m, 1H), 3.48 (m, 1H), 4.01 (m, 1H), 4.35 (m,1H), 5.50 (m, 2H), 7.45 (m, 2H), 7.56-7.61 (m, 3H), 7.89 (m, 2H), 8.02(m, 1H), 8.84 (s, 1H)

MS (ESI): 583 ([M+H]⁺)

1-Naphthyl2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(I-813)

Oxalyl chloride (6.78 g) and a drop of N,N-dimethylformamide are addedto a solution of [3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetic acid(10.8 g) in dichloromethane (150 ml). The reaction mixture is stirred atroom temperature overnight, and excess oxalyl chloride is then removedunder reduced pressure. The residue is redissolved in dichloromethane(50 ml) and added to a solution of4-{4-[(1-naphthyloxy)carbonyl]-1,3-thiazol-2-yl]piperidinium chloride(X-2, 7.25 g) and Hünig base (10.4 g) in dichloromethane (100 ml) at 0°C. The reaction mixture is stirred at room temperature overnight. Afteraddition of conc. ammonium chloride solution, the aqueous phase isseparated off and extracted with ethyl acetate. The combined organicphases are dried over sodium sulfate. The solid is filtered off and thesolvent is removed by distillation. The residue is purifiedchromatographically. This gives 1-naphthyl2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(11.3 g, 64%).

logP (pH 2.7): 3.64

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.70 (bs, 1H), 1.87 (bs, 1H), 2.18(m, 2H), 2.91 (bs, 1H), 3.31 (bs, 1H), 3.48 (m, 1H), 4.03 (bs, 1H), 4.36(bs, 1H), 5.36 (s, 2H), 6.85 (s, 1H), 6.97 (t, 1H), 7.15 (t, 1H), 7.45(dd, 1H), 7.54-7.61 (m, 3H), 7.89 (m, 2H), 8.01 (m, 1H), 8.84 (s, 1H)

MS (ESI): 547 ([M+H]⁺)

Cyclohexyl2-(1-{2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]ethanethioyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(I-854)

At room temperature,2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide (88mg) is added to a solution of cyclohexyl2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(I-811, 200 mg) in 1,2-dimethoxyethane (1 ml) and chloroform (0.4 ml).The reaction mixture is stirred at 70-80° C. overnight. After removal ofthe solvent under reduced pressure, the residue is purifiedchromatographically. This gives cyclohexyl2-(1-{2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]ethanethioyl}piperidin-4-yl)-1,3-thiazole-4-carboxylate(80 mg, 39%).

logP (pH 2.7): 4.23

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.30-1.58 (m, 6H), 1.75-1.92 (m,4H), 2.10-2.30 (m, 4H), 3.32 (m, 1H), 3.50 (m, 2H), 4.39 (m, 1H), 4.93(m, 1H), 5.39 (s, 2H), 5.42 (m, 1H), 6.79 (t, 1H), 6.83 (s, 1H), 7.01(t, 1H), 8.16 (s, 1H)

MS (ESI): 519 ([M+H]⁺)

EXAMPLES

Table 1 shows the compounds of the formula (I) whose use as fungicidesis claimed.

(I)

EX NO R¹ R² R³ R⁴ R⁵ Y¹ X W R⁶ Y² Y³ G R⁷ log p 1 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— H O O —CH₂— trimethylsilyl 2 CF₃ H CH₃ H H O —CH₂CH₂——CH₂— H O O bond cyclohexyl 3 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bondcyclopentyl 3.40* 4 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂—cyclopropyl 5 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂— 2,2-dichloro-cyclopropyl 6 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond 1,2,3,4- 4.01**tetrahydro- naphthalen-1-yl 7 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bonddecahydro- naphthalen-1-yl 8 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond2,3-dihydro- 3.76* 1H-inden-1-yl 9 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O Obond 1-naphthyl 10 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond 2-naphthyl3.84* 11 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂CH₂— morpholin-4-yl 12CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂— 4-fluorophenyl 3.35* 13 CF₃ HCH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂CH₂— piperidin-1-yl 14 CF₃ H CH₃ H HO —CH₂CH₂— —CH₂— H O O —CH₂CH₂— pyrrolidin-1-yl 15 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— H O O —CH₂— phenyl 3.37* 16 CF₃ H CH₃ H H O —CH₂CH₂——CH₂— H O O —CH₂— 4-methyl- piperazin-1-yl 17 CF₃ H CH₃ H H O —CH₂CH₂——CH₂— H O O —CH₂— 4-chlorophenyl 3.73* 18 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂—H O O —CH₂— 4-methylphenyl 4.21* 19 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O—CH₂— 4-methoxy- 3.30* phenyl 20 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O—CH₂— 2,4-dichloro- 3.69* phenyl 21 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O—CH₂— 3,5-dichloro- 4.24* phenyl 22 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O—CH₂— 2,6-dichloro- 3.94* phenyl 23 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O—CH₂— 2-chlorophenyl 3.70* 24 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂—3-chlorophenyl 3.72* 25 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂—3-(trifluoro- 3.81* methyl)phenyl 26 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H OO —CH₂— 3-methylphenyl 27 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂—4-fluorophenyl 4.00* 28 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂—4-nitrophenyl 3.22* 29 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂—4-tert-butyl- 4.57* phenyl 30 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂—phenyl 31 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂— 2-methylphenyl3.62* 32 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂— 4-chlorophenyl 33CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂— 4-methylphenyl 34 CF₃ H CH₃ HH O —CH₂CH₂— —CH₂— H O S —CH₂— 4-methoxy- phenyl 35 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— H O S —CH₂— 2,4-dichloro- phenyl 36 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— H O S —CH₂— 3,5-dichloro- phenyl 37 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— H O S —CH₂— 2,6-dichloro- phenyl 38 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— H O S —CH₂— 2-chlorophenyl 39 CF₃ H CH₃ H H O —CH₂CH₂——CH₂— H O S —CH₂— 3-chlorophenyl 40 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S—CH₂— 3-(trifluoro- methyl)phenyl 41 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H OO —CH(CH₃)— 4-fluorophenyl 3.60* 42 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O—CH(CH₂CH₃)— 4-fluorophenyl 3.89* 43 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H OO —CH₂CH₂— 4-fluorophenyl 3.55* 44 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O Obond phenyl 3.20* 45 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond4-fluorophenyl 3.26* 46 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂—2-methylphenyl 47 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH(CF₃)— phenyl48 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂— 4-nitrophenyl 49 CF₃ H CH₃H H O —CH₂CH₂— —CH₂— H O S —CH₂— 4-tert-butyl- phenyl 50 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— H O S —CH₂— 3-methylphenyl 51 CF₃ H CH₃ H H O —CH₂CH₂——CH₂— H O O bond 3-chlorophenyl 52 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O Obond 4-methylphenyl 53 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond3-chlorophenyl 54 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond3,5-dichloro- phenyl 55 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond3,4-dichloro- phenyl 56 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond2,4-dichloro- phenyl 57 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond2-chlorophenyl 58 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond2,6-dichloro- phenyl 59 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond3-(trifluoro- methyl)phenyl 60 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond3-methylphenyl 61 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond2-methylphenyl 62 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond4-tert-butyl- phenyl 63 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond4-nitrophenyl 64 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S bond phenyl 65 CF₃H CH₃ H H O —CH₂CH₂— —CH₂— H O S bond 4-fluorophenyl 66 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— H O S bond 4-chlorophenyl 67 CF₃ H CH₃ H H O —CH₂CH₂——CH₂— H O S bond 4-methylphenyl 68 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O Sbond 3-chlorophenyl 69 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S bond3,5-dichloro- phenyl 70 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S bond3,4-dichloro- phenyl 71 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S bond2,4-dichloro- phenyl 72 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S bond2-chlorophenyl 73 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S bond2,6-dichloro- phenyl 74 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S bond3-(trifluoro- methyl)phenyl 75 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S bond3-methylphenyl 76 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S bond cyclohexyl4.51* 77 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S bond 1-naphthyl 4.22* 78CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S bond 4-nitrophenyl 79 CF₃ H CH₃ H HO —CH₂CH₂— —CH₂— H O O —CH₂— pyridin-4-yl 80 CF₃ H CH₃ H H O —CH₂CH₂——CH₂— H O O —CH₂— pyridin-2-yl 2.21* 81 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— HO O —CH₂— 2-thienyl 3.22* 82 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S bond2-methylphenyl 83 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S bond4-tert-butyl- phenyl 84 CF₃ H H H H O —CH₂CH₂— —CH₂— H O O —CH₂—trimethylsilyl 3.53* 85 CF₃ H H H H O —CH₂CH₂— —CH₂— H O O bondcyclohexyl 3.42* 86 CF₃ H H H H O —CH₂CH₂— —CH₂— H O O bond cyclopentyl87 CF₃ H H H H O —CH₂CH₂— —CH₂— H O O —CH₂— cyclopropyl 88 CF₃ H H H H O—CH₂CH₂— —CH₂— H O O —CH₂— 2,2-dichloro- cyclopropyl 89 CF₃ H H H H O—CH₂CH₂— —CH₂— H O O bond 1,2,3,4- 3.68* tetrahydro- naphthalen-1-yl 90CF₃ H H H H O —CH₂CH₂— —CH₂— H O O bond decahydro- naphthalen-1-yl 91CF₃ H H H H O —CH₂CH₂— —CH₂— H O O bond 2,3-dihydro- 3.37* 1H-inden-1-yl92 CF₃ H H H H O —CH₂CH₂— —CH₂— H O O bond 1-naphthyl 3.42* 93 CF₃ H H HH O —CH₂CH₂— —CH₂— H O O bond 2-naphthyl 94 CF₃ H H H H O —CH₂CH₂— —CH₂—H O O —CH₂— phenyl 2.99* 95 CF₃ H H H H O —CH₂CH₂— —CH₂— H O O —CH₂—4-fluorophenyl 3.04* 96 CF₃ H H H H O —CH₂CH₂— —CH₂— H O O —CH₂—4-chlorophenyl 97 CF₃ H H H H O —CH₂CH₂— —CH₂— H O O —CH₂—4-methylphenyl 98 CF₃ H H H H O —CH₂CH₂— —CH₂— H O O —CH₂— 4-methoxy-phenyl 99 CF₃ H H H H O —CH₂CH₂— —CH₂— H O O —CH₂— 2,4-dichloro- phenyl100 CF₃ H H H H O —CH₂CH₂— —CH₂— H O O —CH₂— 3,5-dichloro- phenyl 101CF₃ H H H H O —CH₂CH₂— —CH₂— H O O —CH₂— 2,6-dichloro- phenyl 102 CF₃ HH H H O —CH₂CH₂— —CH₂— H O O —CH₂— 2-chlorophenyl 103 CF₃ H H H H O—CH₂CH₂— —CH₂— H O O —CH₂— 3-chlorophenyl 104 CF₃ H H H H O —CH₂CH₂——CH₂— H O O —CH₂— 3-(trifluoro- methyl)phenyl 105 CF₃ H H H H O —CH₂CH₂——CH₂— H O O —CH₂— 3-methylphenyl 106 CF₃ H H H H O —CH₂CH₂— —CH₂— H O O—CH₂— 2-methylphenyl 107 CF₃ H H H H O —CH₂CH₂— —CH₂— H O O —CH₂—4-nitrophenyl 108 CF₃ H H H H O —CH₂CH₂— —CH₂— H O O —CH₂— 4-tert-butyl-phenyl 109 CF₃ H H H H O —CH₂CH₂— —CH₂— H O S —CH₂— phenyl 110 CF₃ H H HH O —CH₂CH₂— —CH₂— H O S —CH₂— 4-fluorophenyl 111 CF₃ H H H H O —CH₂CH₂——CH₂— H O S —CH₂— 4-chlorophenyl 112 CF₃ H H H H O —CH₂CH₂— —CH₂— H O S—CH₂— 4-methylphenyl 113 CF₃ H H H H O —CH₂CH₂— —CH₂— H O S —CH₂—4-methoxy- phenyl 114 CF₃ H H H H O —CH₂CH₂— —CH₂— H O S —CH₂—2,4-dichloro- phenyl 115 CF₃ H H H H O —CH₂CH₂— —CH₂— H O S —CH₂—3,5-dichloro- phenyl 116 CF₃ H H H H O —CH₂CH₂— —CH₂— H O S —CH₂—2,6-dichloro- phenyl 117 CF₃ H H H H O —CH₂CH₂— —CH₂— H O S —CH₂—2-chlorophenyl 118 CF₃ H H H H O —CH₂CH₂— —CH₂— H O S —CH₂—3-chlorophenyl 119 CF₃ H H H H O —CH₂CH₂— —CH₂— H O S —CH₂—3-(trifluoro- methyl)phenyl 120 CF₃ H H H H O —CH₂CH₂— —CH₂— H O S —CH₂—3-methylphenyl 121 CF₃ H H H H O —CH₂CH₂— —CH₂— H O S —CH₂—2-methylphenyl 122 CF₃ H H H H O —CH₂CH₂— —CH₂— H O S —CH₂—4-nitrophenyl 123 CF₃ H H H H O —CH₂CH₂— —CH₂— H O S —CH₂— 4-tert-butyl-phenyl 124 CF₃ H H H H O —CH₂CH₂— —CH₂— H O O —CH(CH₃)— 4-fluorophenyl3.18* 125 CF₃ H H H H O —CH₂CH₂— —CH₂— H O O —CH(CH₃)— 4-fluorophenyl126 CF₃ H H H H O —CH₂CH₂— —CH₂— H O O —CH₂CH₂— 4-fluorophenyl 3.27* 127CF₃ H H H H O —CH₂CH₂— —CH₂— H O O bond phenyl 2.85* 128 CF₃ H H H H O—CH₂CH₂— —CH₂— H O O bond 4-fluorophenyl 2.89* 129 CF₃ H H H H O—CH₂CH₂— —CH₂— H O O bond 4-chlorophenyl 130 CF₃ H H H H O —CH₂CH₂——CH₂— H O O bond 4-methylphenyl 131 CF₃ H H H H O —CH₂CH₂— —CH₂— H O Obond 3-chlorophenyl 132 CF₃ H H H H O —CH₂CH₂— —CH₂— H O O bond3,5-dichloro- phenyl 133 CF₃ H H H H O —CH₂CH₂— —CH₂— H O O bond3,4-dichloro- phenyl 134 CF₃ H H H H O —CH₂CH₂— —CH₂— H O O bond2,4-dichloro- phenyl 135 CF₃ H H H H O —CH₂CH₂— —CH₂— H O O bond2-chlorophenyl 136 CF₃ H H H H O —CH₂CH₂— —CH₂— H O O bond 2,6-dichloro-phenyl 137 CF₃ H H H H O —CH₂CH₂— —CH₂— H O O bond 3-(trifluoro-methyl)phenyl 138 CF₃ H H H H O —CH₂CH₂— —CH₂— H O O bond 3-methylphenyl139 CF₃ H H H H O —CH₂CH₂— —CH₂— H O O bond 2-methylphenyl 140 CF₃ H H HH O —CH₂CH₂— —CH₂— H O O bond 4-tert-butyl- phenyl 141 CF₃ H H H H O—CH₂CH₂— —CH₂— H O O bond 4-nitrophenyl 142 CF₃ H H H H O —CH₂CH₂— —CH₂—H O O —CH₂— pyridin-4-yl 1.32* 143 CF₃ H H H H O —CH₂CH₂— —CH₂— H O O—CH₂— 2-thienyl 2.85* 144 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂—trimethylsilyl 4.28* rine 145 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O Obond cyclohexyl 4.17* rine 146 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O Obond cyclopentyl 3.84* rine 147 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O O—CH₂— cyclopropyl rine 148 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O O—CH₂— 2,2-dichloro- rine propyl 149 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— HO O bond 1,2,3,4- 4.40* rine tetrahydro- naphthalen-1-yl 150 CF₃ chlo-CH₃ H H O —CH₂CH₂— —CH₂— H O O bond decahydro 5.44* rine naphthalen-1-yl151 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O O bond 2,3-dihydro- 4.17*rine 1H-inden-1-yl 152 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O O bond1-naphthyl 4.17* rine 153 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O O bond2-naphthyl 4.17* rine 154 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂—phenyl 3.73* rine 155 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂—4-fluorophenyl 3.73* rine 156 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O O—CH₂— 4-chlorophenyl rine 157 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O O—CH₂— 4-methylphenyl rine 158 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O O—CH₂— 4-methoxy- rine phenyl 159 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H OO —CH₂— 2,3-dichloro- rine phenyl 160 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂—H O O —CH₂— 2,5-dichloro- rine phenyl 161 CF₃ chlo- CH₃ H H O —CH₂CH₂——CH₂— H O O —CH₂— 2,6-dichloro- rine phenyl 162 CF₃ chlo- CH₃ H H O—CH₂CH₂— —CH₂— H O O —CH₂— 2-chlorophenyl rine 163 CF₃ chlo- CH₃ H H O—CH₂CH₂— —CH₂— H O O —CH₂— 3-chlorophenyl rine 164 CF₃ chlo- CH₃ H H O—CH₂CH₂— —CH₂— H O O —CH₂— 3-(trifluoro- rine methyl)phenyl 165 CF₃chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂— 3-methylphenyl rine 166 CF₃chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂— 2-methylphenyl rine 167 CF₃chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂— 4-nitrophenyl rine 168 CF₃chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂— 4-tert-butyl- rine phenyl 169CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂— phenyl rine 170 CF₃ chlo-CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂— 4-fluorophenyl rine 171 CF₃ chlo-CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂— 4-chlorophenyl rine 172 CF₃ chlo-CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂— 4-methylphenyl rine 173 CF₃ chlo-CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂— 4-methoxy- rine phenyl 174 CF₃chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂— 2,4-dichloro- rine phenyl 175CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂— 3,5-dichloro- rine phenyl176 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂— 2,6-dichloro- rinephenyl 177 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂— 2-chlorophenylrine 178 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂— 3-chlorophenylrine 179 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂— 3-(trifluoro-rine methyl)phenyl 180 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂—3-methylphenyl rine 181 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂—2-methylphenyl rine 182 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂—4-nitrophenyl rine 183 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂—4-tert-butyl- rine phenyl 184 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O O—CH(CH₃)— 4-fluorophenyl 3.89* rine 185 CF₃ chlo- CH₃ H H O —CH₂CH₂——CH₂— H O O —CH(CH₂CH₃)— 4-fluorophenyl rine 186 CF₃ chlo- CH₃ H H O—CH₂CH₂— —CH₂— H O O —CH₂CH₂— 4-fluorophenyl 3.94* rine 187 CF₃ chlo-CH₃ H H O —CH₂CH₂— —CH₂— H O O bond phenyl 3.58* rine 188 CF₃ chlo- CH₃H H O —CH₂CH₂— —CH₂— H O O bond 4-fluorophenyl 3.63* rine 189 CF₃ chlo-CH₃ H H O —CH₂CH₂— —CH₂— H O O bond 4-chlorophenyl rine 190 CF₃ chlo-CH₃ H H O —CH₂CH₂— —CH₂— H O O bond 4-methylphenyl rine 191 CF₃ chlo-CH₃ H H O —CH₂CH₂— —CH₂— H O O bond 3-chlorophenyl rine 192 CF₃ chlo-CH₃ H H O —CH₂CH₂— —CH₂— H O O bond 3,5-dichloro- rine phenyl 193 CF₃chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O O bond 3,4-dichloro- rine phenyl 194CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O O bond 2,4-dichloro- rine phenyl195 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O O bond 2-chlorophenyl rine196 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O O bond 2,6-dichloro- rinephenyl 197 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O O bond 3-(trifluoro-rine methyl)phenyl 198 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O O bond3-methylphenyl rine 199 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O O bond2-methylphenyl rine 200 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O O bond4-tert-butyl- rine phenyl 201 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O Obond 4-nitrophenyl rine 202 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O Sbond phenyl rine 203 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O S bond4-fluorophenyl rine 204 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O S bond4-chlorophenyl rine 205 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O S bond4-methylphenyl rine 206 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O S bond3-chlorophenyl rine 207 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O S bond3,5-dichloro- rine phenyl 208 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O Sbond 3,4-dichloro- rine phenyl 209 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— HO S bond 2,4-dichloro- rine phenyl 210 CF₃ chlo- CH₃ H H O —CH₂CH₂——CH₂— H O S bond 2-chlorophenyl rine 211 CF₃ chlo- CH₃ H H O —CH₂CH₂——CH₂— H O S bond 2,6-dichloro- rine phenyl 212 CF₃ chlo- CH₃ H H O—CH₂CH₂— —CH₂— H O S bond 3-(trifluoro- rine methyl)phenyl 213 CF₃ chlo-CH₃ H H O —CH₂CH₂— —CH₂— H O S bond 3-methylphenyl rine 214 CF₃ chlo-CH₃ H H O —CH₂CH₂— —CH₂— H O S bond 2-methylphenyl rine 215 CF₃ chlo-CH₃ H H O —CH₂CH₂— —CH₂— H O S bond 4-tert-butyl- rine phenyl 216 CF₃chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O S bond 4-nitrophenyl rine 217 CF₃chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂— pyridin-4-yl 1.82* rine 218CF₃ chlo CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂— 2-thienyl 3.58* rine 219CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O O —CH₂— trimethylsilyl 3.89* 220 CF₃H CH₃ H H O —CH₂— —CH₂CH₂— H O O bond cyclohexyl 3.74* 221 CF₃ H CH₃ H HO —CH₂— —CH₂CH₂— H O O bond cyclopentyl 3.47* 222 CF₃ H CH₃ H H O —CH₂——CH₂CH₂— H O O —CH₂— cyclopropyl 223 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H OO —CH₂— 2,2-dichloro- cyclopropyl 224 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H OO bond 1,2,3,4- 4.01* tetrahydro- naphthalen-1-yl 225 CF₃ H CH₃ H H O—CH₂— —CH₂CH₂— H O O bond decahydro- 5.08* naphthalen-1-yl 226 CF₃ H CH₃H H O —CH₂— —CH₂CH₂— H O O bond 2,3-dihydro- 3.78* 1H-inden-1-yl 227 CF₃H CH₃ H H O —CH₂— —CH₂CH₂— H O O bond 1-naphthyl 3.75* 228 CF₃ H CH₃ H HO —CH₂— —CH₂CH₂— H O O bond 2-naphthyl 3.84* 229 CF₃ H CH₃ H H O —CH₂——CH₂CH₂— H O O —CH₂— phenyl 3.37* 230 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H OO —CH₂— 4-fluorophenyl 3.37* 231 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O O—CH₂— 4-chlorophenyl 232 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O O —CH₂—4-methylphenyl 233 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O O —CH₂— 4-methoxy-phenyl 234 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O O —CH₂— 2,4-dichloro-phenyl 235 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O O —CH₂— 3,5-dichloro-phenyl 236 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O O —CH₂— 2,6-dichloro-phenyl 237 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O O —CH₂— 2-chlorophenyl 238CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O O —CH₂— 3-chlorophenyl 239 CF₃ H CH₃H H O —CH₂— —CH₂CH₂— H O O —CH₂— 3-(trifluoro- methyl)phenyl 240 CF₃ HCH₃ H H O —CH₂— —CH₂CH₂— H O O —CH₂— 3-methylphenyl 241 CF₃ H CH₃ H H O—CH₂— —CH₂CH₂— H O O —CH₂— 2-methylphenyl 242 CF₃ H CH₃ H H O —CH₂——CH₂CH₂— H O O —CH₂— 4-nitrophenyl 243 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— HO O —CH₂— 4-tert-butyl- phenyl 244 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O S—CH₂— phenyl 245 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O S —CH₂—4-fluorophenyl 246 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O S —CH₂—4-chlorophenyl 247 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O S —CH₂—4-methylphenyl 248 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O S —CH₂— 4-methoxy-phenyl 249 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O S —CH₂— 2,4-dichloro-phenyl 250 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O S —CH₂— 3,5-dichloro-phenyl 251 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O S —CH₂— 2,6-dichloro-phenyl 252 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O S —CH₂— 2-chlorophenyl 253CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O S —CH₂— 3-chlorophenyl 254 CF₃ H CH₃H H O —CH₂— —CH₂CH₂— H O S —CH₂— 3-(trifluoro- methyl)phenyl 255 CF₃ HCH₃ H H O —CH₂— —CH₂CH₂— H O S —CH₂— 3-methylphenyl 256 CF₃ H CH₃ H H O—CH₂— —CH₂CH₂— H O S —CH₂— 2-methylphenyl 257 CF₃ H CH₃ H H O —CH₂——CH₂CH₂— H O S —CH₂— 4-nitrophenyl 258 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— HO S —CH₂— 4-tert-butyl- phenyl 259 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O O—CH(CH₃)— 4-fluorophenyl 3.53* 260 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O O—CH(CH₂CH₃)— 4-fluorophenyl 261 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O O—CH₂CH₃— 4-fluorophenyl 3.63* 262 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O Obond phenyl 3.18* 263 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O O bond4-fluorophenyl 3.27* 264 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O O bond4-chlorophenyl 265 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O O bond4-methylphenyl 266 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O O bond3-chlorophenyl- phenyl 267 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O O bond3,5-dichloro 268 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O O bond 3,4-dichloro-phenyl 269 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O O bond 2,4-dichloro phenyl270 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O O bond 2-chlorophenyl 271 CF₃ HCH₃ H H O —CH₂— —CH₂CH₂— H O O bond 2,6-dichloro- phenyl 272 CF₃ H CH₃ HH O —CH₂— —CH₂CH₂— H O O bond 3-(trifluoro- methyl)phenyl 273 CF₃ H CH₃H H O —CH₂— —CH₂CH₂— H O O bond 3-methylphenyl 274 CF₃ H CH₃ H H O —CH₂——CH₂CH₂— H O O bond 2-methylphenyl 275 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— HO O bond 4-tert-butyl- phenyl 276 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O Obond 4-nitrophenyl 277 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O S bond phenyl278 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O S bond 4-fluorophenyl 279 CF₃ HCH₃ H H O —CH₂— —CH₂CH₂— H O S bond 4-chlorophenyl 280 CF₃ H CH₃ H H O—CH₂— —CH₂CH₂— H O S bond 4-methylphenyl 281 CF₃ H CH₃ H H O —CH₂——CH₂CH₂— H O S bond 3-chlorophenyl 282 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— HO S bond 3,5-dichloro- phenyl 283 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O Sbond 3,4-dichloro- phenyl 284 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O S bond2,4-dichloro- phenyl 285 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O S bond2-chlorophenyl 286 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O S bond2,6-dichloro- phenyl 287 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O S bond3-(trifluoro- methyl)phenyl 288 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O Sbond 3-methylphenyl 289 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O S bond2-methylphenyl 290 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O S bond4-tert-butyl- phenyl 291 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O S bond4-nitrophenyl 292 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O O —CH₂—pyridin-4-yl 1.51* 293 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O O —CH₂—2-thienyl 3.23* 294 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂—trimethylsilyl 295 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond cyclohexyl296 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond cyclopentyl 297 CH₃ H CH₃H H O —CH₂CH₂— —CH₂— H O O —CH₂— cyclopropyl 298 CH₃ H CH₃ H H O—CH₂CH₂— —CH₂— H O O —CH₂— 2,2-dichloro- cyclopropyl 299 CH₃ H CH₃ H H O—CH₂CH₂— —CH₂— H O O bond 1,2,3,4- tetrahydro- naphthalen-1-yl 300 CH₃ HCH₃ H H O —CH₂CH₂— —CH₂— H O O bond decahydro- naphthalen-1-yl 301 CH₃ HCH₃ H H O —CH₂CH₂— —CH₂— H O O bond 2,3-dihydro- 1H-inden-1-yl 302 CH₃ HCH₃ H H O —CH₂CH₂— —CH₂— H O O bond 1-naphthyl 303 CH₃ H CH₃ H H O—CH₂CH₂— —CH₂— H O O bond 2-naphthyl 304 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂—H O O —CH₂— phenyl 305 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂—4-fluorophenyl 306 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂—4-chlorophenyl 307 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂—4-methylphenyl 308 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂— 4-methoxy-phenyl 309 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂— 2,4-dichloro-phenyl 310 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂— 3,5-dichloro-phenyl 311 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂— 2,6-dichloro-phenyl 312 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂— 2-chlorophenyl 313CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂— 3-chlorophenyl 314 CH₃ H CH₃H H O —CH₂CH₂— —CH₂— H O O —CH₂— 3-(trifluoro- methyl)phenyl 315 CH₃ HCH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂— 3-methylphenyl 316 CH₃ H CH₃ H H O—CH₂CH₂— —CH₂— H O O —CH₂— 2-methylphenyl 317 CH₃ H CH₃ H H O —CH₂CH₂——CH₂— H O O —CH₂— 4-nitrophenyl 318 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O—CH₂— 4-tert-butyl- phenyl 319 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S—CH₂— phenyl 320 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂—4-fluorophenyl 321 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂—4-chlorophenyl 322 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂—4-methylphenyl 323 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂— 4-methoxy-phenyl 324 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂— 2,4-dichloro-phenyl 325 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂— 3,5-dichloro-phenyl 326 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂— 2,6-dichloro-phenyl 327 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂— 2-chlorophenyl 328CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂— 3-chlorophenyl 329 CH₃ H CH₃H H O —CH₂CH₂— —CH₂— H O S —CH₂— 3-(trifluoro- methyl)phenyl 330 CH₃ HCH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂— 3-methylphenyl 331 CH₃ H CH₃ H H O—CH₂CH₂— —CH₂— H O S —CH₂— 2-methylphenyl 332 CH₃ H CH₃ H H O —CH₂CH₂——CH₂— H O S —CH₂— 4-nitrophenyl 333 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S—CH₂— 4-tert-butyl- phenyl 334 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O—CH(CH₃)— 4-fluorophenyl 335 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O—CH(CH₂CH₃)— 4-fluorophenyl 336 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O—CH₂CH₂— 4-fluorophenyl 337 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bondphenyl 338 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond 4-fluorophenyl 339CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond 4-chlorophenyl 340 CH₃ H CH₃ HH O —CH₂CH₂— —CH₂— H O O bond 4-methylphenyl 341 CH₃ H CH₃ H H O—CH₂CH₂— —CH₂— H O O bond 3-chlorophenyl 342 CH₃ H CH₃ H H O —CH₂CH₂——CH₂— H O O bond 3,5-dichloro- phenyl 343 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂—H O O bond 3,4-dichloro- phenyl 344 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O Obond 2,4-dichloro- phenyl 345 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond2-chlorophenyl 346 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond2,6-dichloro- phenyl 347 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond3-(trifluoro- methyl)phenyl 348 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O Obond 3-methylphenyl 349 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond2-methylphenyl 350 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond4-tert-butyl- phenyl 351 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond4-nitrophenyl 352 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S bond phenyl 353CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S bond 4-fluorophenyl 354 CH₃ H CH₃ HH O —CH₂CH₂— —CH₂— H O S bond 4-chlorophenyl 355 CH₃ H CH₃ H H O—CH₂CH₂— —CH₂— H O S bond 4-methylphenyl 356 CH₃ H CH₃ H H O —CH₂CH₂——CH₂— H O S bond 3-chlorophenyl 357 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O Sbond 3,5-dichoro- phenyl 358 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S bond3,4-dichloro- phenyl 359 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S bond2,4-dichloro- phenyl 360 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S bond2-chlorophenyl 361 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S bond2,6-dichloro- phenyl 362 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S bond3-(trifluoro- methyl)phenyl 363 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O Sbond 3-methylphenyl 364 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S bond2-methylphenyl 365 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O bondcyclopentyl 366 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O S bond 4-nitrophenyl367 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂— pyridin-4-yl 368 CH₃ HCH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O bond 1,2,3,4- 4.04* tetrahydro-naphthalen-1-yl 369 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂—trimethylsilyl 3.84* 370 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O bondcyclohexyl 3.78* 371 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond4-tert-butyl- phenyl 372 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂—cyclopropyl 3.86* 373 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂—2,2-dichloro- cyclopropyl 374 CH₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂—2-thienyl 375 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O bond decahydro-naphthalen-1-yl 376 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O bond2,3-dihydro- 3.68* 1H-inden-1-yl 377 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂—H O O bond 1-naphthalen 3.82* 378 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H OO bond 2-naphthyl 3.73* 379 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O—CH₂— phenyl 3.19* 380 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂—4-fluorophenyl 381 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂—4-chlorophenyl 382 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂—4-methylphenyl 383 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂—4-methoxy- phenyl 384 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂—2,4-dichloro- phenyl 385 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂—3,5-dichloro- phenyl 386 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂—2,6-dichloro- phenyl 387 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂—2-chlorophenyl 388 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂—3-chlorophenyl 389 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂—3-(trifluoro- methyl)phenyl 390 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O—CH₂— 3-methylphenyl 391 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂—2-methylphenyl 392 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂—4-nitrophenyl 393 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂—4-tert-butyl- phenyl 394 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O S —CH₂—phenyl 395 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O S —CH₂— 4-fluorophenyl396 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O S —CH₂— 4-chlorophenyl 397CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O S —CH₂— 4-methylphenyl 398 CH₃ HCH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O S —CH₂— 4-methoxy- phenyl 399 CH₃ H CH₃CH₃ CH₃ O —CH₂CH₂— —CH₂— H O S —CH₂— 2,4-dichloro- phenyl 400 CH₃ H CH₃CH₃ CH₃ O —CH₂CH₂— —CH₂— H O S —CH₂— 3,5-dichloro- phenyl 401 CH₃ H CH₃CH₃ CH₃ O —CH₂CH₂— —CH₂— H O S —CH₂— 2,6-dichloro- phenyl 402 CH₃ H CH₃CH₃ CH₃ O —CH₂CH₂— —CH₂— H O S —CH₂— 2-chlorophenyl 403 CH₃ H CH₃ CH₃CH₃ O —CH₂CH₂— —CH₂— H O O —CH(CH₃)— 4-fluorophenyl 3.47* 404 CH₃ H CH₃CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O —CH(CH₂CH₃)— 4-fluorophenyl 405 CH₃ H CH₃CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂CH₂— 4-fluorophenyl 3.42* 406 CH₃ HCH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O S —CH₂— 2-methylphenyl 407 CH₃ H CH₃CH₃ CH₃ O —CH₂CH₂— —CH₂— H O S —CH₂— 4-nitrophenyl 408 CH₃ H CH₃ CH₃ CH₃O —CH₂CH₂— —CH₂— H O S —CH₂— 4-tert-butyl- phenyl 409 CH₃ H CH₃ CH₃ CH₃O —CH₂CH₂— —CH₂— H O S —CH₂— 3-chlorophenyl 410 CH₃ H CH₃ CH₃ CH₃ O—CH₂CH₂— —CH₂— H O S —CH₂— 3-(trifluoro- methyl)phenyl 411 CH₃ H CH₃ CH₃CH₃ O —CH₂CH₂— —CH₂— H O S —CH₂— 3-methylphenyl 412 CH₃ H CH₃ CH₃ CH₃ O—CH₂CH₂— —CH₂— H O O bond phenyl 3.06* 413 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂——CH₂— H O O bond 4-fluoropheny 3.21* 414 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂——CH₂— H O O bond 4-chlorophenyl 415 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— HO O bond 4-methylphenyl 416 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O Obond 3-chlorophenyl 417 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O bond3,5-dichloro- phenyl 418 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O bond3,4-dichloro- phenyl 419 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O bond2,4-dichloro- phenyl 420 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O bond2-chlorophenyl 421 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O bond2,6-dichloro- phenyl 422 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O bond3-(trifluoro- phenyl) 423 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O bond3-methylphenyl 424 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O bond2-methylphenyl 425 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O bond4-tert-butyl- phenyl 426 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O bond4-nitrophenyl 427 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O S bond phenyl428 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O S bond 4-fluorophenyl 429 CH₃H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O S bond 4-chlorophenyl 430 CH₃ H CH₃CH₃ CH₃ O —CH₂CH₂— —CH₂— H O S bond 4-methylphenyl 431 CH₃ H CH₃ CH₃ CH₃O —CH₂CH₂— —CH₂— H O S bond 3-chlorophenyl 432 CH₃ H CH₃ CH₃ CH₃ O—CH₂CH₂— —CH₂— H O S bond 3,5-dichloro- phenyl 433 CH₃ H CH₃ CH₃ CH₃ O—CH₂CH₂— —CH₂— H O S bond 3,4-dichloro- phenyl 434 CH₃ H CH₃ CH₃ CH₃ O—CH₂CH₂— —CH₂— H O S bond 2,4-dichloro- phenyl 435 CH₃ H CH₃ CH₃ CH₃ O—CH₂CH₂— —CH₂— H O S bond 2-chlorophenyl 436 CH₃ H CH₃ CH₃ CH₃ O—CH₂CH₂— —CH₂— H O S bond 2,6-dichloro- phenyl 437 CH₃ H CH₃ CH₃ CH₃ O—CH₂CH₂— —CH₂— H O S bond 3-(trifluoro- methyl)phenyl 438 CH₃ H CH₃ CH₃CH₃ O —CH₂CH₂— —CH₂— H O S bond 3-methylphenyl 439 CH₃ H CH₃ CH₃ CH₃ O—CH₂CH₂— —CH₂— H O S bond 2-methylphenyl 440 CH₃ H CH₃ CH₃ CH₃ O—CH₂CH₂— —CH₂— H O S bond 4-tert-butyl- phenyl 441 CH₃ H CH₃ CH₃ CH₃ O—CH₂CH₂— —CH₂— H O S bond 4-nitrophenyl 442 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂——CH₂— H O O —CH₂— pyridin-4-yl 1.33* 443 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂——CH₂— H O O —CH₂— 2-thienyl 3.06* 444 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃O O —CH₂— trimethylsilyl 445 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O O bondcyclohexyl 446 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O O bond cyclopentyl447 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O O —CH₂— cyclopropyl 448 CF₃ HCH₃ H H O —CH₂CH₂— —CH₂— CH₃ O O —CH₂— 2,2-dichloro- cyclopropyl 449 CF₃H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O O bond 1,2,3,4- tetrahydro-naphthalen-1-yl 450 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O O bonddecahydro- naphthalen-1-yl 451 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O Obond 2,3-dihydro- 1H-inden-1-yl 452 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ OO bond 1-naphthyl 453 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O O bond2-naphthyl 454 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O O —CH₂— phenyl 455CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O O —CH₂— 4-fluorophenyl 456 CF₃ HCH₃ H H O —CH₂CH₂— —CH₂— CH₃ O O —CH₂— 4-chlorophenyl 457 CF₃ H CH₃ H HO —CH₂CH₂— —CH₂— CH₃ O O —CH₂— 4-methylphenyl 458 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— CH₃ O O —CH₂— 4-methoxy- phenyl 459 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— CH₃ O O —CH₂— 2,4-dichloro- phenyl 460 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— CH₃ O O —CH₂— 3,5-dichloro- phenyl 461 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— CH₃ O O —CH₂— 2,6-dichloro- phenyl 462 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— CH₃ O O —CH₂— 2-chlorophenyl 463 CF₃ H CH₃ H H O —CH₂CH₂——CH₂— CH₃ O O —CH₂— 3-chlorophenyl 464 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂—CH₃ O O —CH₂— 3-(trifluoro- methyl)phenyl 465 CF₃ H CH₃ H H O —CH₂CH₂——CH₂— CH₃ O O —CH₂— 3-methylphenyl 466 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂—CH₃ O O —CH₂— 2-methylphenyl 467 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O O—CH₂— 4-nitrophenyl 468 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O O —CH₂—4-tert-butyl- phenyl 469 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O S —CH₂—phenyl 470 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O S —CH₂— 4-fluorophenyl471 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O S —CH₂— 4-chlorophenyl 472 CF₃H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O S —CH₂— 4-methylphenyl 473 CF₃ H CH₃ HH O —CH₂CH₂— —CH₂— CH₃ O S —CH₂— 4-methoxy- phenyl 474 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— CH₃ O S —CH₂— 2,4-dichloro- phenyl 475 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— CH₃ O S —CH₂— 3,5-dichloro- phenyl 476 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— CH₃ O S —CH₂— 2,6-dichloro- phenyl 477 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— CH₃ O S —CH₂— 2-chlorophenyl 478 CF₃ H CH₃ H H O —CH₂CH₂——CH₂— CH₃ O S —CH₂— 3-chlorophenyl 479 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂—CH₃ O S —CH₂— 3-(trifluoro- methyl)phenyl 480 CF₃ H CH₃ H H O —CH₂CH₂——CH₂— CH₃ O S —CH₂— 3-methylphenyl 481 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂—CH₃ O S —CH₂— 2-methylphenyl 482 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O S—CH₂— 4-nitrophenyl 483 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O S —CH₂—4-tert-butyl- phenyl 484 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O O—CH(CH₃)— 4-fluorophenyl 485 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O O—CH(CH₂CH₃)— 4-fluorophenyl 486 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O O—CH₂CH₂— 4-fluorophenyl 487 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O O bondphenyl 488 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O O bond 4-fluorophenyl489 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O O bond 4-chlorophenyl 490 CF₃ HCH₃ H H O —CH₂CH₂— —CH₂— CH₃ O O bond 4-methylphenyl 491 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— CH₃ O O bond 3-chlorophenyl 492 CF₃ H CH₃ H H O —CH₂CH₂——CH₂— CH₃ O O bond 3,5-dichloro- phenyl 493 CF₃ H CH₃ H H O —CH₂CH₂——CH₂— CH₃ O O bond 3,4-dichloro- phenyl 494 CF₃ H CH₃ H H O —CH₂CH₂——CH₂— CH₃ O O bond 2,4-dichloro- phenyl 495 CF₃ H CH₃ H H O —CH₂CH₂——CH₂— CH₃ O O bond 2-chlorophenyl 496 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃O O bond 2,6-dichloro- phenyl 497 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O Obond 3-(trifluoro- methyl)phenyl 498 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃O O bond 3-methylphenyl 499 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O O bond2-methylphenyl 500 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O O bond4-tert-butyl- phenyl 501 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O O bond4-nitrophenyl 502 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O S bond phenyl 503CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O S bond 4-fluorophenyl 504 CF₃ H CH₃H H O —CH₂CH₂— —CH₂— CH₃ O S bond 4-chlorophenyl 505 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— CH₃ O S bond 4-methylphenyl 506 CF₃ H CH₃ H H O —CH₂CH₂——CH₂— CH₃ O S bond 3-chlorophenyl 507 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃O S bond 3,5-dichloro- phenyl 508 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O Sbond 3,4-dichloro- phenyl 509 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O Sbond 2,4-dichloro- phenyl 510 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O Sbond 2-chlorophenyl 511 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O S bond2,6-dichloro- phenyl 512 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O S bond3-(trifluoro- methyl)phenyl 513 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O Sbond 3-methylphenyl 514 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O S bond2-methylphenyl 515 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O S bond4-tert-butyl- phenyl 516 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O S bond4-nitrophenyl 517 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O O —CH₂—pyridin-4-yl 518 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O O —CH₂— 2-thienyl519 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— CH₃ O S bond cyclohexyl 520 CF₃ H CH₃H H O —CH₂CH₂— —CH₂— CH₃ O S bond 1-naphthyl 521 CF₃ H CH₃ H H O bond—CH₂CH₂CH₂— H O O —CH₂— trimethylsilyl 522 CF₃ H CH₃ H H O bond—CH₂CH₂CH₂— H O O bond cyclohexyl 523 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— HO O bond cyclopentyl 524 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O O —CH₂—cyclopropyl 525 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O O —CH₂—2,2-dichloro- propyl 526 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O O bond1,2,3,4- tetrahydro- naphthalen-1-yl 527 CF₃ H CH₃ H H O bond—CH₂CH₂CH₂— H O O bond decahydro- naphthalen-1-yl 528 CF₃ H CH₃ H H Obond —CH₂CH₂CH₂— H O O bond 2,3-dihydro- 1H-inden-1-yl 529 CF₃ H CH₃ H HO bond —CH₂CH₂CH₂— H O O bond 1-naphthyl 530 CF₃ H CH₃ H H O bond—CH₂CH₂CH₂— H O O bond 2-naphthyl 531 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— HO O —CH₂— phenyl 532 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O O —CH₂—4-fluorophenyl 533 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O O —CH₂—4-chlorophenyl 534 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O O —CH₂—4-methylphenyl 535 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O O —CH₂—4-methoxy- phenyl 536 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O O —CH₂—2,4-dichloro- phenyl 537 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O O —CH₂—3,5-dichloro- phenyl 538 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O O —CH₂—2,6-dichloro- phenyl 539 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O O —CH₂—2-chlorophenyl 540 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O O —CH₂—3-chlorophenyl 541 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O O —CH₂—3-(trifluoro- methyl)phenyl 542 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O O—CH₂— 3-methylphenyl 543 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O O —CH₂—2-methylphenyl 544 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O O —CH₂—4-nitrophenyl 545 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O O —CH₂—4-tert-butyl- phenyl 546 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O S —CH₂—phenyl 547 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O S —CH₂— 4-fluorophenyl548 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O S —CH₂— 4-chlorophenyl 549 CF₃H CH₃ H H O bond —CH₂CH₂CH₂— H O S —CH₂— 4-methylphenyl 550 CF₃ H CH₃ HH O bond —CH₂CH₂CH₂— H O S —CH₂— 4-methoxy- phenyl 551 CF₃ H CH₃ H H Obond —CH₂CH₂CH₂— H O S —CH₂— 2,4-dichloro- phenyl 552 CF₃ H CH₃ H H Obond —CH₂CH₂CH₂— H O S —CH₂— 3,5-dichloro- phenyl 553 CF₃ H CH₃ H H Obond —CH₂CH₂CH₂— H O S —CH₂— 2,6-dichloro- phenyl 554 CF₃ H CH₃ H H Obond —CH₂CH₂CH₂— H O S —CH₂— 2-chlorophenyl 555 CF₃ H CH₃ H H O bond—CH₂CH₂CH₂— H O S —CH₂— 3-chlorophenyl 556 CF₃ H CH₃ H H O bond—CH₂CH₂CH₂— H O S —CH₂— 3-(trifluoro- methyl)phenyl 557 CF₃ H CH₃ H H Obond —CH₂CH₂CH₂— H O S —CH₂— 3-methylphenyl 558 CF₃ H CH₃ H H O bond—CH₂CH₂CH₂— H O S —CH₂— 2-methylphenyl 559 CF₃ H CH₃ H H O bond—CH₂CH₂CH₂— H O S —CH₂— 4-nitrophenyl 560 CF₃ H CH₃ H H O bond—CH₂CH₂CH₂— H O S —CH₂— 4-tert-butyl- phenyl 561 CF₃ H CH₃ H H O bond—CH₂CH₂CH₂— H O O —CH(CH₃)— 4-fluorophenyl 562 CF₃ H CH₃ H H O bond—CH₂CH₂CH₂— H O O —CH(CH₂CH₃)— 4-fluorophenyl 563 CF₃ H CH₃ H H O bond—CH₂CH₂CH₂— H O O —CH₂CH₂— 4-fluorophenyl 564 CF₃ H CH₃ H H O bond—CH₂CH₂CH₂— H O O bond phenyl 565 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O Obond 4-fluorophenyl 566 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O O bond4-chlorophenyl 567 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O O bond4-methylphenyl 568 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O O bond3-chlorophenyl 569 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O O bond3,5-dichloro- phenyl 570 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O O bond3,4-dichloro- phenyl 571 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O O bond2,4-dichloro phenyl 572 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O O bond2-chlorophenyl 573 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O O bond2,6-dichloro- phenyl 574 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O O bond3-(trifluoro- methyl)phenyl 575 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O Obond 3-methylphenyl 576 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O O bond2-methylphenyl 577 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O O bond4-tert-butyl- phenyl 578 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O O bond4-nitrophenyl 579 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O S bond phenyl 580CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O S bond 4-fluorophenyl 581 CF₃ H CH₃H H O bond —CH₂CH₂CH₂— H O S bond 4-chlorophenyl 582 CF₃ H CH₃ H H Obond —CH₂CH₂CH₂— H O S bond 4-methylphenyl 583 CF₃ H CH₃ H H O bond—CH₂CH₂CH₂— H O S bond 3-chlorophenyl 584 CF₃ H CH₃ H H O bond—CH₂CH₂CH₂— H O S bond 3,5-dichloro- phenyl 585 CF₃ H CH₃ H H O bond—CH₂CH₂CH₂— H O S bond 3,4-dichloro- phenyl 586 CF₃ H CH₃ H H O bond—CH₂CH₂CH₂— H O S bond 2,4-dichloro- phenyl 587 CF₃ H CH₃ H H O bond—CH₂CH₂CH₂— H O S bond 2-chlorophenyl 588 CF₃ H CH₃ H H O bond—CH₂CH₂CH₂— H O S bond 2,6-dichloro- phenyl 589 CF₃ H CH₃ H H O bond—CH₂CH₂CH₂— H O S bond 3-(trifluoro- methyl)phenyl 590 CF₃ H CH₃ H H Obond —CH₂CH₂CH₂— H O S bond 3-methylphenyl 591 CF₃ H CH₃ H H O bond—CH₂CH₂CH₂— H O S bond 2-methylphenyl 592 CF₃ H CH₃ H H O bond—CH₂CH₂CH₂— H O S bond 4-tert-butyl- phenyl 593 CF₃ H CH₃ H H O bond—CH₂CH₂CH₂— H O S bond 4-nitrophenyl 594 CF₃ H CH₃ H H O bond—CH₂CH₂CH₂— H O O —CH₂— pyridin-4-yl 595 CF₃ H CH₃ H H O bond—CH₂CH₂CH₂— H O O —CH₂— 2-thienyl 596 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— HO S bond cyclohexyl 597 CF₃ H CH₃ H H O bond —CH₂CH₂CH₂— H O S bond1-naphthyl 598 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂—trimethysilyl 599 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O bond cyclohexyl600 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O bond cyclopentyl 601 CF₃ HCH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂— cyclopropyl 602 CF₃ H CH₃ H CH₃ O—CH₂CH₂— —CH₂— H O O —CH₂— 2,2-dichloro- cyclopropyl 603 CF₃ H CH₃ H CH₃O —CH₂CH₂— —CH₂— H O O bond 1,2,3,4- tetrahydro- naphthalen-1-yl 604 CF₃H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O bond 1decahydro- napthalen-1-yl 605CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O bond 2,3-dihydro- 1H-inden-1-yl606 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O bond 1-naphthyl 607 CF₃ H CH₃H CH₃ O —CH₂CH₂— —CH₂— H O O bond 2-naphthyl 608 CF₃ H CH₃ H CH₃ O—CH₂CH₂— —CH₂— H O O —CH₂— phenyl 609 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— HO O —CH₂— 4-fluorophenyl 610 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O—CH₂— 4-chlorophenyl 611 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂—4-methylphenyl 612 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂—4-methoxy- phenyl 613 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂—2,4-dichloro- phenyl 614 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂—3,5-dichloro- phenyl 615 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂—2,6-dichloro- phenyl 616 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂—2-chlorophenyl 617 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂—3-chlorophenyl 618 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂—3-(trifluoro- methyl)phenyl 619 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O—CH₂— 3-methylphenyl 620 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂—2-methylphenyl 621 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂—4-nitrophenyl 622 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂—4-tert-butyl- phenyl 623 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O S —CH₂—phenyl 624 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O S —CH₂— 4-fluorophenyl625 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O S —CH₂— 4-chlorophenyl 626 CF₃H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O S —CH₂— 4-methylphenyl 627 CF₃ H CH₃ HCH₃ O —CH₂CH₂— —CH₂— H O S —CH₂— 4-methoxy- phenyl 628 CF₃ H CH₃ H CH₃ O—CH₂CH₂— —CH₂— H O S —CH₂— 2,4-dichloro- phenyl 629 CF₃ H CH₃ H CH₃ O—CH₂CH₂— —CH₂— H O S —CH₂— 3,5-dichloro- phenyl 630 CF₃ H CH₃ H CH₃ O—CH₂CH₂— —CH₂— H O S —CH₂— 2,6-dichloro- phenyl 631 CF₃ H CH₃ H CH₃ O—CH₂CH₂— —CH₂— H O S —CH₂— 2-chlorophenyl 632 CF₃ H CH₃ H CH₃ O —CH₂CH₂——CH₂— H O S —CH₂— 3-chlorophenyl 633 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— HO S —CH₂— 3-(trifluoro- methyl)phenyl 634 CF₃ H CH₃ H CH₃ O —CH₂CH₂——CH₂— H O S —CH₂— 3-methylphenyl 635 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— HO S —CH₂— 2-methylphenyl 636 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O S—CH₂— 4-nitrophenyl 637 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O S —CH₂—4-tert-butyl- phenyl 638 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O—CH(CH₃)— 4-fluorophenyl 639 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O—CH(CH₂CH₂)— 4-fluorophenyl 640 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O—CH₂CH₂— 4-fluorophenyl 641 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O bondphenyl 642 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O bond 4-fluorophenyl643 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O bond 4-chlorophenyl 644 CF₃ HCH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O bond 4-methylphenyl 645 CF₃ H CH₃ H CH₃O —CH₂CH₂— —CH₂— H O O bond 3-chlorophenyl 646 CF₃ H CH₃ H CH₃ O—CH₂CH₂— —CH₂— H O O bond 3,5-dichloro- phenyl 647 CF₃ H CH₃ H CH₃ O—CH₂CH₂— —CH₂— H O O bond 3,4-dichloro- phenyl 648 CF₃ H CH₃ H CH₃ O—CH₂CH₂— —CH₂— H O O bond 2,4-dichloro- phenyl 649 CF₃ H CH₃ H CH₃ O—CH₂CH₂— —CH₂— H O O bond 2-chlorophenyl 650 CF₃ H CH₃ H CH₃ O —CH₂CH₂——CH₂— H O O bond 2,6-dichloro phenyl 651 CF₃ H CH₃ H CH₃ O —CH₂CH₂——CH₂— H O O bond 3-(trifluoro- phenyl) 652 CF₃ H CH₃ H CH₃ O —CH₂CH₂——CH₂— H O O bond 3-methylphenyl 653 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H OO bond 2-methylphenyl 654 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O bond4-tert-butyl- phenyl 655 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O bond4-nitrophenyl 656 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O S bond phenyl 657CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O S bond 4-fluorophenyl 658 CF₃ H CH₃H CH₃ O —CH₂CH₂— —CH₂— H O S bond 4-chlorophenyl 659 CF₃ H CH₃ H CH₃ O—CH₂CH₂— —CH₂— H O S bond 4-methylphenyl 660 CF₃ H CH₃ H CH₃ O —CH₂CH₂——CH₂— H O S bond 3-chlorophenyl 661 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H OS bond 3,5-dichloro- phenyl 662 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O Sbond 3,4-dichloro- phenyl 663 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O Sbond 2,4-dichloro- phenyl 664 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O Sbond 2-chlorophenyl 665 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O S bond2,6-dichloro- phenyl 666 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O S bond3-(trifluoro- methyl)phenyl 667 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O Sbond 3-methylphenyl 668 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O S bond2-methylphenyl 669 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O S bond4-tert-butyl- phenyl 670 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O S bond4-nitrophenyl 671 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂—pyridin-4-yl 672 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O —CH₂— 2-thienyl673 CF₃ H CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O S bond cyclohexyl 674 CF₃ H CH₃H CH₃ O —CH₂CH₂— —CH₂— H O S bond 1-naphthyl 675 (1Z,3Z)-buta- CH₃ H H O—CH₂CH₂— —CH₂— H O O —CH₂— trimethylsilyl 1,3-diene-1,4- diyl 676(1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O O bond cyclohexyl1,3-diene-1,4- diyl 677 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O Obond cyclopentyl 1,3-diene-1,4- diyl 678 (1Z,3Z)-buta- CH₃ H H O—CH₂CH₂— —CH₂— H O O —CH₂— cyclopropyl 1,3-diene-1,4- diyl 679(1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂— 2-dichloro-1,3-diene-1,4- propyl diyl 680 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— HO O bond 1,2,3,4- 1,3-diene-1,4- tetrahydro- diyl naphthalen-1-yl 681(1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O O bond decahydro-1,3-diene-1,4- naphthalen-1-yl diyl 682 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂——CH₂— H O O bond 2,3-dihydro- 1,3-diene-1,4- 1H-inden-1-yl diyl 683(1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O O bond 1-naphthyl1,3-diene-1,4- diyl 684 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O Obond 2-naphthyl 1,3-diene-1,4- diyl 685 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂——CH₂— H O O —CH₂— phenyl 1,3-diene-1,4- diyl 686 (1Z,3Z)-buta- CH₃ H H O—CH₂CH₂— —CH₂— H O O —CH₂— 4-fluorophenyl 1,3-diene-1,4- diyl 687(1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂— 4-chlorophenyl1,3-diene-1,4- diyl 688 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O O—CH₂— 4-methylphenyl 1,3-diene-1,4- diyl 689 (1Z,3Z)-buta- CH₃ H H O—CH₂CH₂— —CH₂— H O O —CH₂— 4-methoxy- 1,3-diene-1,4- phenyl diyl 690(1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂— 2,4-dichloro-1,3-diene-1,4- phenyl diyl 691 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— HO O —CH₂— 3,5-dichloro- 1,3-diene-1,4- phenyl diyl 692 (1Z,3Z)-buta- CH₃H H O —CH₂CH₂— —CH₂— H O O —CH₂— 2,6-dichloro- 1,3-diene-1,4- phenyldiyl 693 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂—2-chlorophenyl 1,3-diene-1,4- diyl 694 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂——CH₂— H O O —CH₂— 3-chlorophenyl 1,3-diene-1,4- diyl 695 (1Z,3Z)-buta-CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂— 3-(trifluoro- 1,3-diene-1,4-methyl)phenyl diyl 696 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O O—CH₂— 3-methylphenyl 1,3-diene-1,4- diyl 697 (1Z,3Z)-buta- CH₃ H H O—CH₂CH₂— —CH₂— H O O —CH₂— 2-methylphenyl 1,3-diene-1,4- diyl 698(1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂— 4-nitrophenyl1,3-diene-1,4- diyl 699 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O O—CH₂— 4-tert-butyl- 1,3-diene-1,4- phenyl diyl 700 (1Z,3Z)-buta- CH₃ H HO —CH₂CH₂— —CH₂— H O S —CH₂— phenyl 1,3-diene-1,4- diyl 701(1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂— 4-fluorophenyl1,3-diene-1,4- diyl 702 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O S—CH₂— 4-chlorophenyl 1,3-diene-1,4- diyl 703 (1Z,3Z)-buta- CH₃ H H O—CH₂CH₂— —CH₂— H O S —CH₂— 4-methylphenyl 1,3-diene-1,4- diyl 704(1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂— 4-methoxy-1,3-diene-1,4- phenyl diyl 705 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— HO S —CH₂— 2,4-dichloro- 1,3-diene-1,4- phenyl diyl 706 (1Z,3Z)-buta- CH₃H H O —CH₂CH₂— —CH₂— H O S —CH₂— 3,5-dichloro- 1,3-diene-1,4- phenyldiyl 707 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂—2,6-dichloro- 1,3-diene-1,4- phenyl diyl 708 (1Z,3Z)-buta- CH₃ H H O—CH₂CH₂— —CH₂— H O S —CH₂— 2-chlorophenyl 1,3-diene-1,4- diyl 709(1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂— 3-chlorophenyl1,3-diene-1,4- diyl 710 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O S—CH₂— 3-(trifluoro- 1,3-diene-1,4- methyl)phenyl diyl 711 (1Z,3Z)-buta-CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂— 3-methylphenyl 1,3-diene-1,4- diyl712 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O S —CH₂— 2-methylphenyl1,3-diene-1,4- diyl 713 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O S—CH₂— 4-nitrophenyl 1,3-diene-1,4- diyl 714 (1Z,3Z)-buta- CH₃ H H O—CH₂CH₂— —CH₂— H O S —CH₂— 4-tert-butyl- 1,3-diene-1,4- phenyl diyl 715(1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH(CH₃)— 4-fluorophenyl1,3-diene-1,4- diyl 716 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O O—CH(CH₂CH₃)— 4-fluorophenyl 1,3-diene-1,4- diyl 717 (1Z,3Z)-buta- CH₃ HH O —CH₂CH₂— —CH₂— H O O —CH₂CH₂— 4-fluorophenyl 1,3-diene-1,4- diyl 718(1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O O bond phenyl 1,3-diene-1,4-diyl 719 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O O bond4-fluorophenyl 1,3-diene-1,4- diyl 720 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂——CH₂— H O O bond 4-chlorophenyl 1,3-diene-1,4- diyl 721 (1Z,3Z)-buta-CH₃ H H O —CH₂CH₂— —CH₂— H O O bond 4-methylphenyl 1,3-diene-1,4- diyl722 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O O bond 3-chlorophenyl1,3-diene-1,4- diyl 723 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O Obond 3,5-dichloro- 1,3-diene-1,4- phenyl diyl 724 (1Z,3Z)-buta- CH₃ H HO —CH₂CH₂— —CH₂— H O O bond 3,4-dichloro- 1,3-diene-1,4- phenyl diyl 725(1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O O bond 2,4-dichloro-1,3-diene-1,4- phenyl diyl 726 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— HO O bond 2-chlorophenyl 1,3-diene-1,4- diyl 727 (1Z,3Z)-buta- CH₃ H H O—CH₂CH₂— —CH₂— H O O bond 2,6-dichloro- 1,3-diene-1,4- phenyl diyl 728(1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O O bond 3-(trifluoro-1,3-diene-1,4- methyl)phenyl diyl 729 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂——CH₂— H O O bond 3-methylphenyl 1,3-diene-1,4- diyl 730 (1Z,3Z)-buta-CH₃ H H O —CH₂CH₂— —CH₂— H O O bond 2-methylphenyl 1,3-diene-1,4- diyl731 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O O bond 4-tert-butyl-1,3-diene-1,4- phenyl diyl 732 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— HO O bond 4-nitrophenyl 1,3-diene-1,4- diyl 733 (1Z,3Z)-buta- CH₃ H H O—CH₂CH₂— —CH₂— H O S bond phenyl 1,3-diene-1,4- diyl 734 (1Z,3Z)-buta-CH₃ H H O —CH₂CH₂— —CH₂— H O S bond 4-fluorophenyl 1,3-diene-1,4- diyl735 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O S bond 4-chlorophenyl1,3-diene-1,4- diyl 736 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O Sbond 4-methylphenyl 1,3-diene-1,4- diyl 737 (1Z,3Z)-buta- CH₃ H H O—CH₂CH₂— —CH₂— H O S bond 3-chlorophenyl 1,3-diene-1,4- diyl 738(1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O S bond 3,5-dichloro-1,3-diene-1,4- phenyl diyl 739 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— HO S bond 3,4-dichloro- 1,3-diene-1,4- phenyl diyl 740 (1Z,3Z)-buta- CH₃H H O —CH₂CH₂— —CH₂— H O S bond 2,4-dichloro- 1,3-diene-1,4- phenyl diyl741 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O S bond 2-chlorophenyl1,3-diene-1,4- diyl 742 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O Sbond 2,6-dichloro- 1,3-diene-1,4- phenyl diyl 743 (1Z,3Z)-buta- CH₃ H HO —CH₂CH₂— —CH₂— H O S bond 3-(trifluoro- 1,3-diene-1,4- methyl)phenyldiyl 744 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O S bond3-methylphenyl 1,3-diene-1,4- diyl 745 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂——CH₂— H O S bond 2-methylphenyl 1,3-diene-1,4- diyl 746 (1Z,3Z)-buta-CH₃ H H O —CH₂CH₂— —CH₂— H O S bond 4-tert-butyl- 1,3-diene-1,4- phenyldiyl 747 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O S bond 4-nitrophenyl1,3-diene-1,4- diyl 748 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O O—CH₂— pyridin-4-yl 1,3-diene-1,4- diyl 749 (1Z,3Z)-buta- CH₃ H H O—CH₂CH₂— —CH₂— H O O —CH₂— 2-thienyl 1,3-diene-1,4- diyl 750(1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O S bond cyclohexyl1,3-diene-1,4- diyl 751 (1Z,3Z)-buta- CH₃ H H O —CH₂CH₂— —CH₂— H O sbond 1-naphthyl 1,3-diene-1,4- diyl 752 CF₃ H CH₃ —CH₂CH₂— O —CH₂CH₂——CH₂— H O O bond cyclohexyl 753 CF₃ H CH₃ —CH₂CH₂— O —CH₂CH₂— —CH₂— H OO bond 1,2,3,4- tetrahydro- naphthalen-1-yl 754 CF₃ H CH₃ —CH₂CH₂— O—CH₂CH₂— —CH₂— H O O bond decahydro- naphthalen-1-yl 755 CF₃ H CH₃—CH₂CH₂— O —CH₂CH₂— —CH₂— H O O bond 2,3-dihydro- 1H-inden-1-yl 756 CF₃H CH₃ —CH₂CH₂— O —CH₂CH₂— —CH₂— H O O bond 1-naphthyl 757 CF₃ H CH₃—CH₂CH₂— O —CH₂CH₂— —CH₂— H O O bond 2-naphthyl 758 CF₃ H CH₃ —CH₂CH₂— O—CH₂CH₂— —CH₂— H O O —CH₂— phenyl 759 CF₃ H CH₃ H cyclo- O —CH₂CH₂——CH₂— H O O bond cyclohexyl propyl 760 CF₃ H CH₃ H cyclo- O —CH₂CH₂——CH₂— H O O bond 1,2,3,4- propyl tetrahydro- naphthalen-1-yl 761 CF₃ HCH₃ H cyclo- O —CH₂CH₂— —CH₂— H O O bond decahydro- propylnaphthalen-1-yl 762 CF₃ H CH₃ H cyclo- O —CH₂CH₂— —CH₂— H O O bond2,3-dihydro- propyl 1H-inden-1-yl 763 CF₃ H CH₃ H cyclo- O —CH₂CH₂——CH₂— H O O bond 1-naphthyl propyl 764 CF₃ H CH₃ H cyclo- O —CH₂CH₂——CH₂— H O O bond 2-naphthyl propyl 765 CF₃ H CH₃ H cyclo- O —CH₂CH₂——CH₂— H O O —CH₂— phenyl propyl 766 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O—CH₂CH₂— tert-butyl 767 CF₃ H H H H O —CH₂CH₂— —CH₂— H O O bond —CH₂CH₂—3.82* 768 CF₃ chlo- CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂CH₂— tert-butylrine 769 CF₃ chlo- CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O bond cyclohexyl4.58* rine 770 CF₃ chlo- CH₃ H CH₃ O —CH₂CH₂— —CH₂— H O O bond1-naphthyl 4.50* rine 771 CF₃ H CF₃ H H O —CH₂CH₂— —CH₂— H O O bond1-naphthyl 4.35* 772 CF₃ H CF₃ H H O —CH₂CH₂— —CH₂— H O O bondcyclohexyl 4.39* 773 CF₃ H H H CH₃ O —CH₂CH₂— —CH₂— H O O bond1-naphthyl 3.87* 774 CF₃ H H H CH₃ O —CH₂CH₂— —CH₂— H O O bondcyclohexyl 3.88* 775 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂—3,4-dichloro- 4.09* phenyl 776 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O—CH₂— 4-(trifluoro- 3.86* methyl)phenyl 777 CF₃ H phenyl H H O —CH₂CH₂——CH₂— H O O bond 1-naphthyl 4.50* 778 CF₃ H ethyl H H O —CH₂CH₂— —CH₂— HO O bond 1-naphthyl 779 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂—(E)-2- 3.74* phenylethenyl 780 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O—CH₂— pyridin-3-yl 1.74* 781 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bondquinolin-7-yl 2.42* 782 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bondquinolin-8-yl 2.88* 783 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂—1-naphthyl 3.90* 784 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂—2-naphthyl 3.92* 785 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH(CH₃)—1-naphthyl 4.16* 786 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH(CH₃)—2-naphthyl 4.18* 787 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂—phenylethynyl 3.70* 788 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bondcycloheptyl 4.09* 789 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond 1,2,3,4-tetrahydro- naphthalen-2-yl 790 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O Obond 5,6,7,8- 4.21* tetrahydro- naphthalen-1-yl 791 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— H O O bond 2,3-dihydro- 3.67* 1H-inden-2-yl 792 CF₃ H CH₃H H O —CH₂CH₂— —CH₂— H O O bond 5,6,7,8- 4.30* tetrahydro-naphthalen-1-yl 793 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bondquinolin-6-yl 2.37* 794 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bondisoquinolin-5-yl 2.18* 795 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond(1R)-1,2,3,4- 4.06* tetrahydro- naphthalen-1-yl 796 CH₃ H di- H H O—CH₂CH₂— —CH₂— H O O bond cyclohexyl 3.28* fluoro- methyl 797 CH₃ H CH₃CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O bond 5-methyl-2- 5.51* (propan-2-yl)cyclohexyl 798 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O bond1-ethynyl- 3.28* cyclopentyl 799 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H OO —CH(CH₂CH₃)— (1Z)-prop- 3.78* 1-en-1-yl 800 CH₃ H CH₃ CH₃ CH₃ O—CH₂CH₂— —CH₂— H O O bond (1S,2R)-1,7,7- 5.08* trimethyl- bicyclo[2.2.1]hept-2-yl 801 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O bondhex-1-en-3-yl 3.78* 802 CH₃ H CH₃ CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O bond3-methyl-5- 5.58* (propan-2- yl)cyclohexyl 803 CH₃ H CH₃ CH₃ CH₃ O—CH₂CH₂— —CH₂— H O O —CH₂CH₂— dimethylamino 1.03* 804 CH₃ H CH₃ CH₃ CH₃O —CH₂CH₂— —CH₂— H O O bond 1-ethynyl- 3.73* cyclohexyl 805 CH₃ H CH₃CH₃ CH₃ O —CH₂CH₂— —CH₂— H O O —CH(CH₃)— CF₃ 806 CH₃ H CH₃ CH₃ CH₃ O—CH₂CH₂— —CH₂— H O O —CH₂— heptan-3-yl 5.08* 807 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— H O O bond quinolin-5-yl 2.59* 808 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— H O O bond diphenylmethyl 4.17* 809 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— H O O bond 1,3-benzoxazol- 2.81* 4-yl 810 ethyl H ethyl HH O —CH₂CH₂— —CH₂— H O O bond cyclohexyl 811 di- H di- H H O —CH₂CH₂——CH₂— H O O bond cyclohexyl 3.64* fluoro- fluoro- methyl methyl 812ethyl H ethyl H H O —CH₂CH₂— —CH₂— H O O bond 1-naphthyl 813 di- H di- HH O —CH₂CH₂— —CH₂— H O O bond 1-naphthyl 3.64* fluoro- fluoro- methylmethyl 814 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond 2-methoxy- 3.17*phenyl 815 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond cyclopropyl- 3.87*(phenyl)methyl 816 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond2,6-dimethoxy- 3.12* phenyl 817 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O—CH₂— 2-methoxy- 3.44* phenyl 818 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O—CH₂— 2,4,6-trichloro- 4.53* phenyl 819 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— HO O —CH₂— 4-(trifluoro- 3.99* methoxy)phenyl 820 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— H O O —CH₂— 2-bromophenyl 3.80* 821 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— H O O bond biphenyl-2-yl 3.96* 822 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— H O O bond biphenyl-2-yl 4.16* 823 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— H O O bond biphenyl-2-yl 4.17* 824 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— H O O bond 3-phenoxy- 4.18* phenyl 825 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— H O O bond 4-phenoxy- 4.14* phenyl 826 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— H O O bond 1-ethynyl- 3.76* cyclohexyl 827 CF₃ H CH₃ H HO —CH₂CH₂— —CH₂— H O O bond 1-cyano- 3.33* cyclohexyl 828 CF₃ H CH₃ H HO —CH₂CH₂— —CH₂— H O O bond 4-tert-butyl- 5.19* cyclohexyl 829 CF₃ H CH₃H H O —CH₂CH₂— —CH₂— H O O bond 5-methyl-2- 5.22* (propan-2-yl)-cyclohexyl 830 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond 1,4-dioxaspiro2.90* [4.5]dec-8-yl 831 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O bond2,6-dimethyl- 4.40* cyclohexyl 832 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O Obond 2-methyl- 4.12* cyclohexyl 833 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O Obond octyl 5.02* 834 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂—2,4-dimethoxy- 3.33* phenyl 835 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O—CH₂— 2,4,6-trifluoro 3.53* phenyl 836 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— HO O —CH₂— 2-(trifluoro- 3.84* methyl)phenyl 837 CF₃ H CH₃ H H O —CH₂CH₂——CH₂— H O O —CH₂— 2-(trifluoro- 3.95* methoxy)phenyl 838 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— H O O —CH₂— CH₃ 839 H CF₃ CH₃ H H O —CH₂CH₂— —CH₂— H O O—CH₂— CH₃ 840 CF₃ H H H H O —CH₂CH₂— —CH₂— H O O —CH₂— CH₃ 841 CF₃ chlo-CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂— CH₃ rine 842 CH₃ H CH₃ CH₃ CH₃ O—CH₂CH₂— —CH₂— H O O —CH₂— CH₃ 843 CF₃ H CH₃ H H O —CH₂— —CH₂CH₂— H O O—CH₂— CH₃ 844 CF₃ H di- H H O —CH₂CH₂— —CH₂— H O O bond 1-naphthylfluoro- methyl 845 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂—2-[1-methoxy- 2-(methyl amino)-2-oxo- ethyl]phenyl 846 CF₃ H CH₃ H H O—CH₂CH₂— —CH₂— H O O —CH₂— 2-[(methyl- amino)-(oxo) acetyl]phenyl 847tBu H CF₃ H H O —CH₂CH₂— —CH₂— H O O —CH₂— cyclohexyl 4.75* 848 CF₃ HtBu H H O —CH₂CH₂— —CH₂— H O O —CH₂— cyclohexyl 4.51* 849 tBu H CF₂CF₃ HH O —CH₂CH₂— —CH₂— H O O —CH₂— cyclohexyl 5.08* 850 CF₂CF₃ H tBu H H O—CH₂CH₂— —CH₂— H O O —CH₂— cyclohexyl 4.94* 851 iPr H CF₃ H H O —CH₂CH₂——CH₂— H O O —CH₂— cyclohexyl 4.35* 852 ethyl H CF₃ H H O —CH₂CH₂— —CH₂—H O O —CH₂— cyclohexyl 3.99* 853 CF₃ H CH₃ H H O —CH₂CH₂— —CH₂— H O Obond (1S)-1,2,3,4- 4.06* tetrahydro- naphthalen-1-yl 854 di- H di- H H S—CH₂CH₂— —CH₂— H O O bond cyclohexyl 4.23* fluoro- fluoro- methyl methylThe logP values were measured according to EEC directive 79/831 AnnexV.A8 by HPLC (High Performance Liquid Chromatography) or reversed-phasecolumns (C 18), using the methods below: **The determination in theacidic range is carried out at pH 2.3 using the mobile phases 0.1%aqueous phosphoric acid and acetonitrile linear gradient from 10%acetonitrile to 95% acetonitrile. *The LC-MS determination in the acidicrange is carried out at pH 2.7 using the mobile phases 0.1% aqueousformic acid and acetonitrile (contains 0.1% formic acid) linear gradientfrom 10% acetonitrile to 95% acetonitrile ***The LC-MS determination inthe neutral range is carried out at pH 7.8 using the mobile phases 0.001molar ammonium bicarbonate solution and acetonitrile linear gradientfrom 10% acetonitrile to 95% acetonitrile.

The calibration is carried out using unbranched alkan-2-ones (having 3to 16 carbon atoms) with known logP values (determination of the logPvalues by the retention times using linear interpolation between twosuccessive alkanones). The lambda-maX values were determined in themaxima of the chromatographic signals using the UV spectra from 200 nmto 400 nm.

USE EXAMPLES Example A Phytophthora Test (Tomato)/Protective

Solvent: 24.5 parts by weight of acetone

-   -   24.5 parts by weight of dimethylacetamide        Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated application rate. After thespray coating has dried on, the plants are inoculated with an aqueousspore suspension of Phytophthora infestans. The plants are then placedin an incubation cabin at about 20° C. and 100% relative atmospherichumidity.

Evaluation is carried out 3 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

In this test, the compounds according to the invention of the formulaebelow show, at an active compound concentration of 100 ppm, an efficacyof 70% or more.

Ex. Nos. 44, 45, 8, 10, 766, 772, 771, 774, 773, 18, 20, 19, 775, 17,23, 24, 776, 29, 21, 26, 28, 15, 31, 25, 778, 81, 3, 779, 781, 782, 783,784, 785, 788, 790, 789, 791, 792, 795, 794, 796, 811, 813

Example B Plasmopara Test (Grapevine)/Protective

Solvent: 24.5 parts by weight of acetone

-   -   24.5 parts by weight of dimethylacetamide        Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated application rate. After thespray coating has dried on, the plants are inoculated with an aqueousspore suspension of Plasmopara viticola and then remain in an incubationcabin at about 20° C. and 100% relative atmospheric humidity for 1 day.The plants are then placed in a greenhouse at about 21° C. and about 90%atmospheric humidity for 4 days. The plants are then moistened andplaced in an incubation cabin for 1 day.

Evaluation is carried out 6 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

In this test, the compounds according to the invention of the formulaebelow show, at an active compound concentration of 100 ppm, an efficacyof 70% or more.

Ex. Nos. 44, 45, 8, 10, 766, 772, 771, 774, 773, 18, 20, 19, 775, 17,23, 24, 776, 21, 26, 28, 15, 31, 25, 778, 81, 3, 779, 781, 782, 783,784, 785, 788, 790, 789, 791, 792, 795, 794, 796, 811, 813

Example C Phytophthora Test (Tomato)/Protective

Solvent: 24.5 parts by weight of acetone

-   -   24.5 parts by weight of dimethylacetamide        Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated application rate. After thespray coating has dried on, the plants are inoculated with an aqueousspore suspension of Phytophthora infestans. The plants are then placedin an incubation cabin at about 20° C. and 100% relative atmospherichumidity.

Evaluation is carried out 3 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

TABLE Phytophthora test (tomato)/protective Active compound Activecompound application Efficacy Known from WO2007014290 rate in ppm in %

10 65 According to the invention:

Ex. 23 10 94

Example D Plasmopara Test (Grapevine)/Protective

Solvent: 24.5 parts by weight of acetone

-   -   24.5 parts by weight of dimethylacetamide        Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated application rate. After thespray coating has dried on, the plants are inoculated with an aqueousspore suspension of Plasmopara viticola and then remain in an incubationcabin at about 20° C. and 100% relative atmospheric humidity for 1 day.The plants are then placed in a greenhouse at about 21° C. and about 90%atmospheric humidity for 4 days. The plants are then moistened andplaced in an incubation cabin for 1 day.

Evaluation is carried out 6 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

TABLE Plasmopara test (grapevine)/protective Active compound Activecompound application Efficacy Known from WO2007014290 rate in ppm in %

1 72 According to the invention:

Ex. 6 1 91

Example E Plasmopara Test (Grapevine)/Curative

Solvent: 24.5 parts by weight of acetone

-   -   24.5 parts by weight of dimethylacetamide        Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for curative activity, young plants are inoculated with anaqueous spore suspension of Plasmopara viticola. The plants remain in anincubation cabin at about 20° C. and 100% relative atmospheric humidityfor 24 hours, and after a further 24 hours at about 21° C. and about 90%relative atmospheric humidity, the plants are sprayed with the activecompound preparation at the stated application rate.

5 days after the inoculation, the plants are moistened and placed in anincubation cabin for 1 day.

Evaluation is carried out 6 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

TABLE Plasmopara test (grapevine)/curative Active compound Activecompound application Efficacy Known from WO2007014290 rate in ppm in %

100 37 According to the invention:

Ex. 6 100 84

1. A compound of formula (I)

in which the symbols have the following meanings: R¹ and R³independently of one another are H, C₁-C₄-alkyl, C₂-C₄-alkenyl,C₂-C₄-alkynyl, C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkyl, C₁-C₄-alkoxy,C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, halogen, hydroxyl, cyano or phenyl,R² is H, phenyl, C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-alkynyl,C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl,C₁-C₄ haloalkoxy, formyl, CR⁸═NOR⁹, halogen, hydroxyl, cyano or NR¹⁰R¹¹,or R¹ and R² or R² and R³ together with the carbon atoms to which theyare attached form a 5- to 7-membered unsubstituted or substituted,partially saturated or unsaturated cycle which may contain up to twofurther heteroatoms selected from the group consisting of N, O and S,where two oxygen atoms are not adjacent, possible substituentsindependently of one another being selected from the group consisting ofC₁-C₄-alkyl, hydroxyl, oxo and halogen, R⁴ and R⁵ independently of oneanother are H, C₁-C₄-alkyl, C₃-C₆-cycloalkyl or C₁-C₄-haloalkyl, or R⁴and R⁵ together with the carbon atom to which they are attached form a3- to 6-membered saturated cycle which may contain up to two heteroatomsselected from the group consisting of N and O, where two oxygen atomsare not adjacent, Y¹, and Y² are oxygen, Y³ is sulfur or oxygen, X is adirect bond or an unsubstituted or substituted C₁- to C₃-carbon chain,where the carbon atoms carry, independently of one another, H, methyl oroxo as substituents, W is an unsubstituted or substituted C₁- toC₃-carbon chain, where the carbon atoms carry, independently of oneanother, H, methyl or oxo as substituents, R⁶ is H, C₁-C₄-alkyl,C₁-C₄-haloalkyl, CONR¹⁰R¹¹, (C₁-C₄-alkoxy)carbonyl, COOH, NR¹⁰R¹¹,halogen or cyano, G is (C(R¹²)₂)_(m), where m=0 to 6, R⁷ isunsubstituted or substituted C₅-C₁₀-alkyl, C₂-C₁₆-alkenyl,C₂-C₁₆-alkynyl, C₃-C₁₅-cycloalkyl, C₅-C₁₅-cycloalkenyl,C₃-C₁₅-heterocyclyl, aryl, hetaryl or Si(C₁-C₄-alkyl)₃, possiblesubstituents independently of one another are selected from: halogen,cyano, nitro, nitroso, C₁-C₄-alkyl, C₁-C₄-haloalkyl, aryl-C₁-C₃-alkyl,aryl-C₁-C₃-haloalkyl, hydroxyl, oxo, C₁-C₄-alkoxy,O(C₁-C₆-alkyl)_(m)OC₁-C₆-alkyl, O—C₃-C₆-cycloalkyl, O-phenyl,C₁-C₄-haloalkoxy, SH, C₁-C₄-thioalkyl, C₁-C₄-thiohaloalkyl, S-phenyl,SO₂—C₁-C₆-alkyl, SO₂—C₁-C₆-haloalkyl, SO—C₁-C₆-alkyl,SO—C₁-C₆-haloalkyl, CO₂H, (C₁-C₄-alkyl)carbonyl,(C₁-C₄-haloalkyl)carbonyl, formyl, CR₈═NOR₉, CONR₁₀R₁₁,(C₁-C₄-alkoxy)carbonyl, COOH, NR₁₀R₁₁, cyclopropylamino, CH₂COCH₃,(CH₂)_(m)O—C₁-C₆-alkyl, CH₂OH, CH₂SMe, (CH₂)₂SMe, C₃-C₆-cycloalkyl,1-methoxycyclopropyl, 1-chlorocyclopropyl, cyclohexylmethyl,C₂-C₆-alkenyl, C₂-C₆-alkynyl, Si(C₁-C₄-alkyl)₃, phenyl or benzyl, or twoadjacent substituents form an optionally methyl- or halogen-substituteddioxolane or dioxane ring, R⁸, R⁹, R¹⁰, and R¹¹ independently of oneanother are H, C₁-C₃-alkyl or cyclopropyl, or R¹⁰ and R¹¹ together withthe nitrogen atom to which they are attached form a 3- to 6-memberedsaturated cycle which may contain up to one further heteroatom selectedfrom the group consisting of N and O, R¹² is identical or differentindependently of one another H, chlorine, fluorine, C₁-C₃-alkyl,C₁-C₃-alkoxy, C₃-C₆-cycloalkyl or trifluoromethyl, or two or four R¹²,in each case on two adjacent carbon atoms, are direct bonds, or anagrochemically active salt thereof.
 2. The compound of the formula (I)as claimed in claim 1, in which one or more of the symbols have one ofthe following meanings: R¹ is methyl, ethyl, 1-methylethyl,1,1-dimethylethyl, difluoromethyl, trifluoromethyl or pentafluoroethyl,R² is H or chlorine, R³ is H, methyl, 1,1-dimethylethyl, difluoromethyl,trifluoromethyl, pentafluoroethyl or phenyl, R⁴ is H or methyl, R⁵ is Hor methyl, Y¹ is oxygen, Y² is oxygen, Y³ is sulfur or oxygen, X is CH₂or CH₂CH₂, W is CH₂ or CH₂CH₂, R⁶ is H, G is a direct bond, CH₂, CH₂CH₂,CH(CH₃) or CH₂(CH₂CH₃), R⁷ is heptan-3-yl, octyl, (1Z)-prop-1-en-1-yl,(E)-2-phenylethenyl, hex-1-en-3-yl, diphenylmethyl,1,2,3,4-tetrahydronaphthalen-1-yl,(1R)-1,2,3,4-tetrahydronaphthalen-1-yl,(1S)-1,2,3,4-tetrahydronaphthalen-1-yl,1,2,3,4-tetrahydronaphthalen-2-yl, 5,6,7,8-tetrahydronaphthalen-1-yl,5,6,7,8-tetrahydronaphthalen-2-yl, decahydronaphthalen-1-yl,1,4-dioxaspiro[4.5]dec-8-yl, 2,3-dihydro-1H-inden-1-yl,2,3-dihydro-1H-inden-2-yl, cyclopropyl, cyclopentyl,1-ethynylcyclopentyl, cyclohexyl, 2-methylcyclohexyl,2,6-dimethylcyclohexyl, 4-tert-butylcyclohexyl,5-methyl-2-(propan-2-yl)cyclohexyl, 3-methyl-5-(propan-2-yl)cyclohexyl,1-cyanocyclohexyl, 1-ethynylcyclohexyl, cycloheptyl,cyclopropyl(phenyl)methyl,(1S,2R)-1,7,7-trimethylbicyclo[2.2.1]hept-2-yl, phenyl, 2-chlorophenyl,3-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 2,6-dichlorophenyl,3,4-dichlorophenyl, 3,5-dichlorophenyl, 2,4,6-trichlorophenyl,2,4,6-trifluorophenyl, 2-methoxyphenyl, 4-methoxyphenyl,2,4-dimethoxyphenyl, 2,6-dimethoxyphenyl, 2-methylphenyl,3-methylphenyl, 4-methylphenyl, 4-nitrophenyl,2-(trifluoromethyl)phenyl, 3-(trifluoromethyl)phenyl,4-(trifluoromethyl)phenyl, 2-(trifluoromethoxy)phenyl,4-(trifluoromethoxy)phenyl, 4-tert-butylphenyl, biphenyl-2-yl,biphenyl-3-yl, biphenyl-4-yl, 3-phenoxyphenyl, 4-phenoxyphenyl,1-naphthyl, 2-naphthyl, phenylethynyl, 2-thienyl, pyridin-2-yl,pyridin-3-yl, pyridin-4-yl, quinolin-5-yl, quinolin-6-yl, quinolin-7-yl,quinolin-8-yl, isoquinolin-5-yl, 1,3-benzoxazol-4-yl, trifluoromethyl,dimethylamino or trimethylsilyl, or an agrochemically active saltthereof.
 3. A method for controlling phytopathogenic harmful fungi,comprising applying a compound of the formula (I) as claimed in claim 1to phytopathogenic harmful fungi, their habitat, or combinationsthereof.
 4. A composition for controlling phytopathogenic harmful fungi,comprising at least one compound of the formula (I) as claimed in claim1 and an extender, or a surfactant, or combinations thereof. 5.(canceled)
 6. A process for preparing a compound of the formula (I)according to claim 1, which comprises at least one of steps c. to e.below: c. converting a compound of the formula (IV) or (VII) into acompound of the formula (III) or (VIII), in each case by hydrolysis inthe presence of a base and, optionally, in the presence of a solvent,according to the reaction scheme below:

where

for compounds of the formulae (IV) and (III), Q=acetyl,C₁-C₄-alkoxycarbonyl, benzyl or benzyloxycarbonyl, for compounds of theformulae (VII) and (VIII), and W, X, R¹, R², R³, R⁴, R⁵ and R⁶ are asdefined in claim 1; d. reacting a compound of the formula (III) or(VIII) with a compound of the formula (II) to give a compound of theformula (I) or (IX), in each case, optionally, in the presence of acoupling agent, a base and a solvent, according to the reaction schemebelow:

where

for compounds of the formulae (III) and (I), Q=acetyl,C₁-C₄-alkoxycarbonyl, benzyl or benzyloxycarbonyl, for compounds of theformulae (VIII) and (IX), Z═OH or chlorine, and W, X, Y³, G, R¹, R², R³,R⁴, R⁵, R⁶ and R⁷ are as defined in claim 1; e. converting a compound ofthe formula (I) into a compound of the formula (I) in the presence of asulfurizing agent and, optionally, in the presence of a solvent,according to the reaction scheme below:

where Y¹=sulfur or oxygen, Y²=sulfur or oxygen, wherein at least one ofY¹ and Y² is sulfur, and W, X, Y³, G, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ areas defined in claim
 1. 7. A compound of formula (XVI-1), (XVI-2),(XVI-3), (XVI-4) or (XVI-5):

or a salt thereof.
 8. A compound of formula (V-1), (V-2), (V-3), (V-4)or (V-5):

or a salt thereof.
 9. A compound of the formula (IV-1), (IV-2) or(IV-3):

or a salt thereof.
 10. A compound of formula (III-1), (III-2) or(III-3):

in which Z═OH or chlorine or a salt thereof.
 11. A compound of formula(IX):

in which PG is acetyl, C₁-C₂-alkoxycarbonyl, benzyl orbenzyloxycarbonyl; W is an unsubstituted or substituted C₁- to C₃-carbonchain, where the carbon atoms carry, independently of one another, H,methyl or oxo as substituents; X is a direct bond or an unsubstituted orsubstituted C₁- to C₃-carbon chain, where the carbon atoms carry,independently of one another, H, methyl or oxo as substituents; Y³ issulfur or oxygen; G is (C(R¹²)₂)_(m); R¹² is identical or differentindependently of one another H, chlorine, fluorine, C₁-C₃-alkyl,C₁-C₃-alkoxy, C₃-C₆-cycloalkyl or trifluoromethyl, or two or four R¹²,in each case on two adjacent carbon atoms, are direct bonds where m=0 to6; R⁶ is H, C₁-C₄-alkyl, C₁-C₄-haloalkyl, CONR¹⁰R¹¹,(C₁-C₄-alkoxy)carbonyl, COOH, NR¹⁰R¹¹, halogen or cyano; R¹⁰ and R¹¹independently of one another are H, C₁-C₃-alkyl or cyclopropyl; R⁷ isunsubstituted or substituted C₅-C₁₀-alkyl, C₂-C₁₆-alkenyl,C₂-C₁₆-alkynyl, C₃-C₁₅-cycloalkyl, C₅-C₁₅-cycloalkenyl,C₃-C₁₅-heterocyclyl, aryl, hetaryl or Si(C₁-C₄-alkyl)₃, possiblesubstituents independently of one another are selected from: halogen,cyano, nitro, nitroso, C₁-C₄-alkyl, C₁-C₄-haloalkyl, aryl-C₁-C₃-alkyl,aryl-C₁-C₃-haloalkyl, hydroxyl, oxo, C₁-C₄-alkoxy, alkyl,O—C₃-C₆-cycloalkyl, O-phenyl, C₁-C₄-haloalkoxy, SH, C₁-C₄-thioalkyl,C₁-C₄-thiohaloalkyl, S-phenyl, SO₂—C₁-C₆-alkyl, SO₂—C₁-C₆-haloalkyl,SO—C₁-C₆: C₁-C₃-alkyl, C₁-C₃-alkoxy, C₃-C₆-cycloalkyl ortrifluoromethyl, or a salt thereof.
 12. A compound of formula (X):

in which W is an unsubstituted or substituted C₁- to C₃-carbon chain,where the carbon atoms carry, independently of one another, H, methyl oroxo as substituents; X is a direct bond or an unsubstituted orsubstituted C₁- to C₃-carbon chain, where the carbon atoms carry,independently of one another, H, methyl or oxo as substituents; Y³ issulfur or oxygen; G is (C(R¹²)₂)_(m); R¹² is identical or differentindependently of one another H, chlorine, fluorine, C₁-C₃-alkyl,C₁-C₃-alkoxy, C₃-C₆-cycloalkyl or trifluoromethyl, or two or four R¹²,in each case on two adjacent carbon atoms, are direct bonds where m=0 to6; R⁶ is H, C₁-C₄-alkyl, C₁-C₄-haloalkyl, CONR¹⁰R¹¹,(C₁-C₄-alkoxy)carbonyl, COOH, NR¹⁰R¹¹, halogen or cyano; R¹⁰ and R¹¹independently of one another are H, C₁-C₃-alkyl or cyclopropyl; R⁷ isunsubstituted or substituted C₅-C₁₀-alkyl, C₂-C₁₆-alkenyl,C₂-C₁₆-alkynyl, C₃-C₁₅-cycloalkyl, C₅-C₁₅-cycloalkenyl,C₃-C₁₅-heterocyclyl, aryl, hetaryl or Si(C₁-C₄-alkyl)₃; possiblesubstituents independently of one another are selected from: halogen,cyano, nitro, nitroso, C₁-C₄-alkyl, C₁-C₄-haloalkyl, aryl-C₁-C₃-alkyl,aryl-C₁-C₃-haloalkyl, hydroxyl, oxo, C₁-C₄-alkoxy,O(C₁-C₆-alkyl)_(m)OC₁-C₆-alkyl, O—C₃-C₆-cycloalkyl, O-phenyl,C₁-C₄-haloalkoxy, SH, C₁-C₄-thioalkyl, C₁-C₄-thiohaloalkyl, S-phenyl,SO₂—C₁-C₆-alkyl, SO₂—C₁-C₆-haloalkyl, SO—C₁-C₆-C₁-C₃-alkyl,C₁-C₃-alkoxy, C₃-C₆-cycloalkyl or trifluoromethyl, or a salt thereof.13. A method for controlling phytopathogenic harmful fungi on seed,comprising applying a compound of the formula (I) as claimed in claim 1on seed.
 14. A method for controlling phytopathogenic harmful fungi ontransgenic plants, comprising applying a compound of the formula (I) asclaimed in claim 1 on transgenic plants, their habitat, or combinationsthereof.
 15. A compound of formula IX-1 or IX-2 according to claim 11,


16. A compound of formula X-1 or X-2 according to claim 12,